Synergistic surfactant blends

ABSTRACT

Synergistic surfactant blends are disclosed. In one aspect, the blend comprises an anionic surfactant and a metathesis-based cationic surfactant comprising a quaternized derivative. The quaternized derivative is a quaternized fatty amine, quaternized fatty amidoamine, imidazoline quat, or esteramine quat made from a metathesis-derived C10-C17 monounsaturated acid or its ester derivative. Also disclosed are synergistic surfactant blends comprising a cationic surfactant and a metathesis-based anionic surfactant comprising a sulfonated derivative. The sulfonated derivative is a fatty ester sulfonate, fatty acid sulfonate, sulfoestolide, fatty amide sulfonate, sulfonated fatty ester alkoxylate, imidazoline quat sulfonate, sulfonated amidoamine oxide, or sulfonated amidoamine betaine. The synergistic blends have a negative β value or a reduced interfacial tension (IFT) when compared with an expected IFT value calculated from the individual surfactant components. Blends of the invention also exhibit surprisingly favorable solubility profiles. The surfactant blends are useful for laundry detergents, dish detergents, household or industrial cleaners, personal care products, agricultural products, building materials, oil recovery compositions, emulsion polymers, and other practical applications.

FIELD OF THE INVENTION

The invention relates to blends of cationic and anionic surfactants, andmore particularly to blends that exhibit synergy and have favorablesolubility profiles.

BACKGROUND OF THE INVENTION

Surfactants and blends of surfactants are important components oflaundry detergents, dish detergents, household or industrial cleaners,personal care products, agricultural products, building materials, oilrecovery compositions, emulsion polymers, and other products. Blends ofsurfactants are used frequently to achieve performance characteristicsthat are not easy to accomplish with a single surfactant type. Forexample, blends of anionic with nonionic or amphoteric surfactants arecommonly used to formulate two-in-one shampoo and conditionerformulations for hair care.

When two surfactants used together provide unexpected surfacecharacteristics compared with what could have been predicted based onsumming their individual contributions, the combination exhibitssynergy. Synergistic surfactant blends offer economic advantages becausethe benefits of each component can be realized at lower concentrations.Synergism has been quantified in mathematical terms. See, for example,the background discussion of U.S. Pat. No. 5,360,571, which explains therelationship between critical micelle concentration and β^(m), the mixedmicelle parameter. As the reference explains, negative β valuescorrespond to synergism, and more negative values indicate greatersynergy.

Synergy can also be identified by measuring interfacial tension (IFT) asa function of surfactant blend composition. Minima in such plotscorrespond to blends having the highest synergy level. See, for example,U.S. Pat. No. 5,441,541 or 5,472,455, particularly Example 2 and FIG. 6.The '541 patent teaches that blends of certain cationic and anionicsurfactants exhibit synergism, and the effect is maximized whenequimolar amounts of the surfactants are used. According to thepatentees, the “strong synergism in surface tension reductioneffectiveness and efficiency implies the formation of a new activemoiety” ('541 patent at Ex. 2).

Strong synergy has been observed in blends of cationic and anionicsurfactants. However, the ability to form complexes and achieve asynergistic effect has tradeoffs, particularly with regard tosolubility. Blends of cationic and anionic surfactants are often avoidedbecause the complexes tend to precipitate, especially when the blendsare diluted with water. According to U.S. Pat. No. 6,306,805, “mostanionic-cationic surfactant mixtures studied are insoluble or onlyslightly soluble in water. . . . At present, very few anionic-cationicsurfactant mixtures have been found which produce clear solution phasesover a wide concentration range at equimolar composition” ('805 patentat col. 3, II. 3-13). The reference acknowledges the high probability ofsynergism in mixtures of anionic and cationic surfactants, but qualifiesits value: “However . . . the variations in surfactant type and sizethat produce progressively more negative β values unfortunately areaccompanied by decreasing solubility. Hence, anionic-cationic synergismis limited by the formation of an insoluble salt, which typically occurswhen the combined number of carbon atoms in the chains of bothsurfactants totals more than about twenty” ('805 patent at col. 3, II.20-43). To overcome the solubility issue, the patentees use a ternaryblend that includes a semi-polar nonionic, ethoxylated alkanolamide, oramphoteric/zwitterionic component as a “bridging surfactant.”

Improvements in metathesis catalysts (see J. C. Mol, Green Chem. 4(2002) 5) have enabled the manufacture of reduced chain length,monounsaturated feedstocks, which are valuable for making detergents andsurfactants, from C₁₆ to C₂₂-rich natural oils such as soybean oil orpalm oil. Soybean oil and palm oil can be more economical than, forexample, coconut oil, which is a traditional starting material formaking detergents. We recently described how to synthesize a variety ofvaluable anionic and cationic surfactants from metathesis-based,monounsaturated feedstocks (see, e.g., copending PCT Int. Appl. Nos.US11/57595, US11/57596, US11/57597, US11/57602, US11/57605, andUS11/57609, all filed 25 Oct. 2011). Among the cationic surfactants, forinstance, we described quaternized fatty amines and quaternized fattyamidoamines made from metathesis-derived C₁₀-C₁₇ monounsaturated acidsand their ester derivatives. Among the anionic surfactants, we describedsulfonated esters, sulfoestolides, and fatty amide sulfonates made frommetathesis-derived C₁₀-C₁₇ monounsaturated acids, octadecene-1,18-dioicacid, or their ester derivatives.

Given the tendency of combinations of anionic and cationic surfactantsto precipitate from aqueous solutions, particularly when their combinedcarbon number exceeds twenty, it was unclear whether surfactants madefrom monounsaturated, metathesis-based feedstocks (with typical carbonnumbers 10-18 for one portion of the complex) would offer any advantagefor cationic-anionic surfactant blends, even if the blends happened todemonstrate synergy. However, the potential benefits of synergy invitedus to explore this possibility.

In sum, the surfactant industry would benefit from the availability ofnew cationic-anionic surfactant blends, particularly blends that exhibitsynergy and could be used to improve the performance and/or economics ofend-use applications. Valuable blends would take advantage of thenow-available, methathesis-based feedstocks based on soybean oil, palmoil, or other renewable resources. Ideally, the blends would avoid thesolubility issues that have, until now, limited their applicability.

SUMMARY OF THE INVENTION

In one aspect, the invention relates to a synergistic surfactant blendcomprising a metathesis-based cationic surfactant. The blend comprises:(a) an anionic surfactant; and (b) a cationic surfactant comprising aquaternized derivative. The quaternized derivative is a quaternizedfatty amine, quaternized fatty amidoamine, imidazoline quat, oresteramine quat. The quaternized derivative is made from ametathesis-derived C₁₀-C₁₇ monounsaturated acid or its ester derivative.The blend exhibits synergy as evidenced by a negative β value or areduced interfacial tension (IFT) when compared with an expected IFTvalue calculated from the individual surfactant components.

In another aspect, the invention relates to a synergistic surfactantblend comprising a metathesis-based anionic surfactant. This blendcomprises: (a) a cationic surfactant; and (b) an anionic surfactantcomprising a sulfonated derivative. The sulfonated derivative is a fattyester sulfonate, fatty acid sulfonate, sulfoestolide, fatty amidesulfonate, sulfonated fatty ester alkoxylate, imidazoline quatsulfonate, sulfonated amidoamine oxide, or sulfonated amidoaminebetaine. The sulfonated derivative is made from a metathesis-derivedC₁₀-C₁₇ monounsaturated acid, octadecene-1,18-dioic acid, or their esterderivatives. The blend exhibits synergy based on the negative β or IFTcomparisons as noted above.

In addition to the negative β or reduced IFT values, blends of theinvention exhibit surprisingly favorable solubility profiles. Thesurfactant blends should be valuable for a wide range of applications,including (among others) laundry detergents, dish detergents, householdor industrial cleaners, personal care products, agricultural products,building materials, oil recovery compositions, and emulsion polymers.

DETAILED DESCRIPTION OF THE INVENTION

I. Synergistic Surfactant Blend: Metathesis-Based Cationic Surfactant

One synergistic surfactant blend of the invention comprises ametathesis-based cationic surfactant. The blend comprises an anionicsurfactant and a cationic surfactant comprising a quaternizedderivative. The quaternized derivative is a quaternized fatty amine,quaternized fatty amidoamine, imidazoline quat, or esteramine quat. Thequaternized derivative is made from a metathesis-derived C₁₀-C₁₇monounsaturated acid or its ester derivative.

As used herein, “monounsaturated” refers to compositions that compriseprincipally species having a single carbon-carbon double bond but mayalso include a minor proportion of one or more species that have two ormore carbon-carbon double bonds. The skilled person will appreciate thatit is not necessary and often impractical to produce a purely“monounsaturated” species, and that mixtures comprising principally (butnot exclusively) monounsaturated acids, esters, and derivatives arecontemplated as within the scope of the invention.

A. The Anionic Surfactant

Suitable anionic surfactants are well known in the art. They include,for example, alkyl sulfates, alkyl ether sulfates, olefin sulfonates,α-sulfonated alkyl esters (particularly α-sulfonated methyl esters),α-sulfonated alkyl carboxylates, alkyl aryl sulfonates, sulfoacetates,sulfosuccinates, isethionates, taurates, alkane sulfonates, andalkylphenol alkoxylate sulfates, and the like, and mixtures thereof.

In particular, anionic surfactants useful herein include those disclosedin McCutcheon's Detergents & Emulsifiers (M. C. Publishing, N. AmericanEd., 1993); Schwartz et al., Surface Active Agents, Their Chemistry andTechnology (New York: Interscience, 1949); and in U.S. Pat. Nos.4,285,841 and 3,919,678, the teachings of which are incorporated hereinby reference.

Suitable anionic surfactants include salts (e.g., sodium, potassium,ammonium, and substituted ammonium salts such as mono-, di-, andtriethanolamine salts) of anionic sulfate, sulfonate, carboxylate andsarcosinate surfactants. Other suitable anionic surfactants includeisethionates (e.g., acyl isethionates), N-acyl taurates, fatty amides ofmethyl tauride, alkyl succinates, glutamates, sulfoacetates, andsulfosuccinates, monoesters of sulfosuccinate (especially saturated andunsaturated C₁₂-C₁₈ monoesters), diesters of sulfosuccinate (especiallysaturated and unsaturated C₆-C₁₄ diesters), and N-acyl sarcosinates.Resin acids and hydrogenated resin acids are also suitable, such asrosin, hydrogenated rosin, and resin acids and hydrogenated resin acidspresent in or derived from tallow oil.

Suitable anionic surfactants include linear and branched primary andsecondary alkyl sulfates, alkyl ethoxysulfates, fatty oleyl glycerolsulfates, alkyl phenol ethoxylate sulfates, alkyl phenol ethylene oxideether sulfates, the C₅-C₁₇ acyl-N—(C₁-C₄ alkyl) and —N—(C₁-C₂hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharidessuch as the sulfates of alkylpolyglucoside. Preferred alkyl sulfatesinclude C₈-C₂₂, more preferably C₈-C₁₆, alkyl sulfates. Preferred alkylethoxysulfates are C₈-C₂₂, more preferably C₈-C₁₆, alkyl sulfates thathave been ethoxylated with from 0.5 to 30, more preferably from 1 to 30,moles of ethylene oxide per molecule.

Other suitable anionic surfactants include salts of C₅-C₂₀ linearalkylbenzene sulfonates, alkyl ester sulfonates, C₆-C₂₂ primary orsecondary alkane sulfonates, C₆-C₂₄ olefin sulfonates, alkyl glycerolsulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerolsulfonates, and any mixtures thereof.

Suitable anionic surfactants include C₈-C₂₂, preferably C₈-C₁₈, alkylsulfonates and C₈-C₂₂, preferably C₁₂-C₁₈, α-olefin sulfonates. Suitableanionic carboxylate surfactants include alkyl ethoxy carboxylates, alkylpolyethoxy polycarboxylate surfactants and soaps (“alkyl carboxyls”).Preferred sulfosuccinates are C₈-C₂₂ sulfosuccinates, preferablymono-C₁₀-C₁₆ alkyl sulfosuccinates such as disodium laurethsulfosuccinate.

Suitable anionic surfactants include sarcosinates of the formulaRCON(R₁)CH₂COOM, wherein R is a C₅-C₂₂ linear or branched alkyl oralkenyl group, R₁ is C₁-C₄ alkyl and M is an ion. Preferred sarcosinatesinclude myristyl and oleoyl methyl sarcosinates as sodium salts. Mostpreferably, the sarcosinate is a C₁₀-C₁₆ sarcosinate.

Suitable anionic surfactants include alkyl sulfoacetates of the formulaRO(CO)CH₂SO₃M, wherein R is C₁₂-C₂₀ alkyl and M is an ion, preferablylauryl and myristyl sulfoacetates as sodium salts.

Many suitable anionic surfactants are commercially available from StepanCompany and are sold under the Alpha-Step®, Bio-Soft®, Bio-Terge®,Cedepal@, Nacconol®, Ninate®, Polystep®, Steol®, Stepanate®, Stepanol®,Stepantan®, and Steposol® trademarks. For further examples of suitableanionic surfactants, see U.S. Pat. No. 6,528,070, the teachings of whichare incorporated herein by reference.

B. The Metathesis-Derived Cationic Surfactant

The second component of the inventive blend is a cationic surfactantcomprising a quaternized derivative. The quaternized derivative is aquaternized fatty amine, quaternized fatty amidoamine, imidazoline quat,or esteramine quat. The quaternized derivative is made from ametathesis-derived C₁₀-C₁₇ monounsaturated acid or its ester derivative.

The skilled person will appreciate that “ester derivative” hereencompasses other acyl equivalents, such as acid chlorides, acidanhydrides, or the like, in addition to the more common lower alkylesters.

In one aspect, the ester derivative is a lower alkyl ester, especially amethyl ester. The lower alkyl esters are preferably generated bytransesterifying a metathesis-derived triglyceride. For example,cross-metathesis of a natural oil with an olefin, followed by removal ofunsaturated hydrocarbon metathesis products by stripping, and thentransesterification of the modified oil component with a lower alkanolunder basic conditions provides a mixture of unsaturated lower alkylesters. The unsaturated lower alkyl ester mixture can be used “as is” tomake quaternized derivatives or it can be purified to isolate particularalkyl esters prior to making the quaternized derivatives. The C₁₀-C₁₇monounsaturated acid or its ester derivative used as a reactant isderived from metathesis of a natural oil. Traditionally, thesematerials, particularly the short-chain acids and derivatives (e.g.,9-decylenic acid or 9-dodecylenic acid) have been difficult to obtainexcept in lab-scale quantities at considerable expense.

However, because of the recent improvements in metathesis catalysts,these acids and their ester derivatives are now available in bulk atreasonable cost. Thus, the C₁₀-C₁₇ monounsaturated acids and esters areconveniently generated by cross-metathesis of natural oils with olefins,preferably α-olefins, and particularly ethylene, propylene, 1-butene,1-hexene, 1-octene, and the like.

Preferably, at least a portion of the C₁₀-C₁₇ monounsaturated acid has“Δ⁹” unsaturation, i.e., the carbon-carbon double bond in the C₁₀-C₁₇acid is at the 9-position with respect to the acid carbonyl. In otherwords, there are preferably seven carbons between the acid carbonylgroup and the olefin group at C9 and C10. For the C₁₁ to C₁₇ acids, analkyl chain of 1 to 7 carbons, respectively is attached to C10.Preferably, the unsaturation is at least 1 mole % trans-Δ⁹, morepreferably at least 25 mole % trans-Δ⁹, more preferably at least 50 mole% trans-Δ⁹, and even more preferably at least 80% trans-Δ⁹. Theunsaturation may be greater than 90 mole %, greater than 95 mole %, oreven 100% trans-Δ⁹. In contrast, naturally sourced fatty acids that haveΔ⁹ unsaturation, e.g., oleic acid, usually have 100% cis-isomers.

Although a high proportion of trans-geometry (particularly trans-Δ⁹geometry) may be desirable in the metathesis-derived quaternizedderivatives, the skilled person will recognize that the configurationand the exact location of the carbon-carbon double bond will depend onreaction conditions, catalyst selection, and other factors. Metathesisreactions are commonly accompanied by isomerization, which may or maynot be desirable. See, for example, G. Djigoue and M. Meier, Appl.Catal. A: General 346 (2009) 158, especially FIG. 3. Thus, the skilledperson might modify the reaction conditions to control the degree ofisomerization or alter the proportion of cis- and trans-isomersgenerated. For instance, heating a metathesis product in the presence ofan inactivated metathesis catalyst might allow the skilled person toinduce double bond migration to give a lower proportion of producthaving trans-Δ⁹ geometry.

An elevated proportion of trans-isomer content (relative to the usualall-cis configuration of the natural monounsaturated acid or ester)imparts different physical properties to quaternized derivatives madefrom them, including, for example, modified physical form, meltingrange, compactability, and other important properties. These differencesshould allow formulators that the quaternized derivatives greaterlatitude or expanded choice as they use the metathesis-derived cationicsurfactants in cleaners, fabric treatment, personal care, agriculturaluses, and other end uses.

Suitable metathesis-derived C₁₀-C₁₇ monounsaturated acids include, forexample, 9-decylenic acid (9-decenoic acid), 9-undecenoic acid,9-dodecylenic acid (9-dodecenoic acid), 9-tridecenoic acid,9-tetradecenoic acid, 9-pentadecenoic acid, 9-hexadecenoic acid,9-heptadecenoic acid, and the like, and their ester derivatives.

Usually, cross-metathesis or self-metathesis of the natural oil isfollowed by separation of an olefin stream from a modified oil stream,typically by distilling out the more volatile olefins. The modified oilstream is then reacted with a lower alcohol, typically methanol, to giveglycerin and a mixture of alkyl esters. This mixture normally includessaturated C₆-C₂₂ alkyl esters, predominantly C₁₆-C₁₈ alkyl esters, whichare essentially spectators in the metathesis reaction. The rest of theproduct mixture depends on whether cross- or self-metathesis is used.When the natural oil is self-metathesized and then transesterified, thealkyl ester mixture will include a C₁₈ unsaturated diester. When thenatural oil is cross-metathesized with an α-olefin and the productmixture is transesterified, the resulting alkyl ester mixture includes aC₁₀ unsaturated alkyl ester and one or more C₁₁ to C₁₇ unsaturated alkylester coproducts in addition to the glycerin by-product. The terminallyunsaturated C₁₀ product is accompanied by different coproducts dependingupon which α-olefin(s) is used as the cross-metathesis reactant. Thus,1-butene gives a C₁₂ unsaturated alkyl ester, 1-hexene gives a C₁₄unsaturated alkyl ester, and so on. The C₁₀ unsaturated alkyl ester isreadily separated from the C₁₁ to C₁₇ unsaturated alkyl ester and eachis easily purified by fractional distillation. These alkyl esters areexcellent starting materials for making the quaternized derivatives.

Natural oils suitable for use as a feedstock to generate the C₁₀-C₁₇monounsaturated acid or its ester derivative from self-metathesis orcross-metathesis with olefins are well known. Suitable natural oilsinclude vegetable oils, algal oils, animal fats, tall oils, derivativesof the oils, and combinations thereof. Thus, suitable natural oilsinclude, for example, soybean oil, palm oil, rapeseed oil, coconut oil,palm kernel oil, sunflower oil, safflower oil, sesame oil, corn oil,olive oil, peanut oil, cottonseed oil, canola oil, castor oil, tallow,lard, poultry fat, fish oil, and the like. Soybean oil, palm oil,rapeseed oil, and mixtures thereof are preferred natural oils.

Genetically modified oils, e.g., high-oleate soybean oil or geneticallymodified algal oil, can also be used. Preferred natural oils havesubstantial unsaturation, as this provides a reaction site for themetathesis process for generating olefins. Particularly preferred arenatural oils that have a high content of unsaturated fatty groupsderived from oleic acid. Thus, particularly preferred natural oilsinclude soybean oil, palm oil, algal oil, and rapeseed oil.

A modified natural oil, such as a partially hydrogenated vegetable oil,can be used instead of or in combination with the natural oil. When anatural oil is partially hydrogenated, the site of unsaturation canmigrate to a variety of positions on the hydrocarbon backbone of thefatty ester moiety. Because of this tendency, when the modified naturaloil is self-metathesized or is cross-metathesized with the olefin, thereaction products will have a different and generally broaderdistribution compared with the product mixture generated from anunmodified natural oil. However, the products generated from themodified natural oil are similarly converted to quaternized derivatives.

An alternative to using a natural oil as a feedstock to generate theC₁₀-C₁₇ monounsaturated acid or its ester derivative fromself-metathesis or cross-metathesis with olefins is a monounsaturatedfatty acid obtained by the hydrolysis of a vegetable oil or animal fat,or an ester or salt of such an acid obtained by esterification of afatty acid or carboxylate salt, or by transesterification of a naturaloil with an alcohol. Also useful as starting compositions arepolyunsaturated fatty esters, acids, and carboxylate salts. The saltscan include an alkali metal (e.g., Li, Na, or K); an alkaline earthmetal (e.g., Mg or Ca); a Group 13-15 metal (e.g., B, Al, Sn, Pb, orSb), or a transition, lanthanide, or actinide metal. Additional suitablestarting compositions are described at pp. 7-17 of PCT application WO2008/048522, the contents of which are incorporated by reference herein.

The other reactant in the cross-metathesis reaction is an olefin.Suitable olefins are internal or α-olefins having one or morecarbon-carbon double bonds. Mixtures of olefins can be used. Preferably,the olefin is a monounsaturated C₂-C₁₀ α-olefin, more preferably amonounsaturated C₂-C₈ α-olefin. Preferred olefins also include C₄-C₉internal olefins. Thus, suitable olefins for use include, for example,ethylene, propylene, 1-butene, cis- and trans-2-butene, 1-pentene,isohexylene, 1-hexene, 3-hexene, 1-heptene, 1-octene, 1-nonene,1-decene, and the like, and mixtures thereof.

Cross-metathesis is accomplished by reacting the natural oil and theolefin in the presence of a homogeneous or heterogeneous metathesiscatalyst. The olefin is omitted when the natural oil isself-metathesized, but the same catalyst types are generally used.Suitable homogeneous metathesis catalysts include combinations of atransition metal halide or oxo-halide (e.g., WOCl₄ or WCl₆) with analkylating cocatalyst (e.g., Me₄Sn). Preferred homogeneous catalysts arewell-defined alkylidene (or carbene) complexes of transition metals,particularly Ru, Mo, or W. These include first and second-generationGrubbs catalysts, Grubbs-Hoveyda catalysts, and the like. Suitablealkylidene catalysts have the general structure:

M[X¹X²L¹L²(L³)_(n)]═C_(m)═C(R¹)R²

where M is a Group 8 transition metal, L¹, L², and L³ are neutralelectron donor ligands, n is 0 (such that L³ may not be present) or 1, mis 0, 1, or 2, X¹ and X² are anionic ligands, and R¹ and R² areindependently selected from H, hydrocarbyl, substituted hydrocarbyl,heteroatom-containing hydrocarbyl, substituted heteroatom-containinghydrocarbyl, and functional groups. Any two or more of X¹, X², L¹, L²,L³, R¹ and R² can form a cyclic group and any one of those groups can beattached to a support.

First-generation Grubbs catalysts fall into this category where m=n=0and particular selections are made for n, X¹, X², L¹, L², L³, R¹ and R²as described in U.S. Pat. Appl. Publ. No. 2010/0145086 (“the '086publication”), the teachings of which related to all metathesiscatalysts are incorporated herein by reference.

Second-generation Grubbs catalysts also have the general formuladescribed above, but L¹ is a carbene ligand where the carbene carbon isflanked by N, O, S, or P atoms, preferably by two N atoms. Usually, thecarbene ligand is party of a cyclic group. Examples of suitablesecond-generation Grubbs catalysts also appear in the '086 publication.

In another class of suitable alkylidene catalysts, L¹ is a stronglycoordinating neutral electron donor as in first- and second-generationGrubbs catalysts, and L² and L³ are weakly coordinating neutral electrondonor ligands in the form of optionally substituted heterocyclic groups.Thus, L² and L³ are pyridine, pyrimidine, pyrrole, quinoline, thiophene,or the like.

In yet another class of suitable alkylidene catalysts, a pair ofsubstituents is used to form a bi- or tridentate ligand, such as abiphosphine, dialkoxide, or alkyldiketonate. Grubbs-Hoveyda catalystsare a subset of this type of catalyst in which L² and R² are linked.Typically, a neutral oxygen or nitrogen coordinates to the metal whilealso being bonded to a carbon that is α-, β-, or γ- with respect to thecarbene carbon to provide the bidentate ligand. Examples of suitableGrubbs-Hoveyda catalysts appear in the '086 publication.

The structures below provide just a few illustrations of suitablecatalysts that may be used:

Heterogeneous catalysts suitable for use in the self- orcross-metathesis reaction include certain rhenium and molybdenumcompounds as described, e.g., by J. C. Mol in Green Chem. 4 (2002) 5 atpp. 11-12. Particular examples are catalyst systems that include Re₂O₇on alumina promoted by an alkylating cocatalyst such as a tetraalkyl tinlead, germanium, or silicon compound. Others include MoCl₃ or MoCl₅ onsilica activated by tetraalkyltins.

For additional examples of suitable catalysts for self- orcross-metathesis, see U.S. Pat. No. 4,545,941, the teachings of whichare incorporated herein by reference, and references cited therein.

General Note Regarding Chemical Structures:

As the skilled person will recognize, products made in accordance withthe invention are typically mixtures of cis- and trans-isomers. Exceptas otherwise indicated, all of the structural representations providedherein show only a trans-isomer. The skilled person will understand thatthis convention is used for convenience only, and that a mixture of cis-and trans-isomers is understood unless the context dictates otherwise.(The “C18-” series of products in the examples below, for instance, arenominally 100% trans-isomers whereas the “Mix-” series are nominally80:20 trans-/cis-isomer mixtures.) Structures shown often refer to aprincipal product that may be accompanied by a lesser proportion ofother components or positional isomers. For instance, sulfonation orsulfitation processes often give mixtures of sultones, alkanesulfonates,and alkenesulfonates, in addition to isomerized products. Thus, thestructures provided represent likely or predominant products. Chargesmay or may not be shown but are understood, as in the case of amineoxide structures. Counterions, as in quaternized compositions, are notusually included, but they are understood by the skilled person from thecontext.

As noted above, the metathesis-based cationic surfactants comprisequaternized derivatives. The quarternized derivatives includequaternized fatty amines, quaternized fatty amidoamines, imidazolinequats, and esteramine quats.

1. Quaternized Fatty Amines and Fatty Amidoamines

Fatty amines used to make the quaternized fatty amines can be made byreacting a metathesis-derived C₁₀-C₁₇ monounsaturated acid or its esterderivative with a secondary amine, followed by reduction of theresulting fatty amide. They can also be made reducing ametathesis-derived acid or ester derivative to a fatty alcohol, followedby amination of the fatty alcohol. Thus, intermediates to the fattyamines are metathesis-derived fatty alcohols or fatty amides.

Suitable secondary amines have a hydrogen and two hydrocarbyl groupsattached to nitrogen. The hydrocarbyl groups are preferably linear,branched, or cyclic C₁-C₂₀ alkyl, C₆-C₂₀ aryl, or C₇-C₂₀ arylalkyl. Morepreferably, both of the hydrocarbyl groups are C₁-C₆ alkyl groups.Suitable secondary amines include, for example, N,N-dimethylamine,N,N-diethylamine, N,N,-dipropylamine, diisopropylamine,N,N-dibutylamine, N-methyl-N-cyclohexylamine, N-methyl-N-phenylamine,N-methyl-N-benzylamine, or the like, and mixtures thereof.N,N-Dimethylamine is cost-effective and is particularly preferred.

Suitable secondary amines include etheramines. Thus, amines that arereaction products of ammonia or primary amines and an alkylene oxide,for example 0.1 to 20 molar equivalents of ethylene oxide, propyleneoxide, or the like, can be used. The amine can be, for instance, amonoalkylated derivative of a Jeffamine® M series polyether amine(product of Huntsman). In some instances of using an etheramine, it maybe necessary to mask any hydroxyl functionality as an appropriatederivative, either before or after formation of the amide, so as toenable the subsequent reduction of this amide.

The reactants are typically reacted, with or without a catalyst underconditions effective to convert the starting acid, ester, or otherderivative to an amide. The reaction temperature is typically within therange of 40° C. to 300° C., preferably from 50° C. to 250° C., and morepreferably from 50° C. to 200° C.

Reduction of the fatty amide to give a terminal amine is accomplishedusing well-known methods, including reactions with a hydride reducingagent (boranes, aluminum hydrides, borohydrides, or the like), orcatalytic hydrogenation. Suitable reducing reagents include, forexample, borane, borane dimethylsulfide, sodium borohydride/iodine,lithium cyanoborohydride, aluminum hydride, lithium aluminum hydride,diisobutylaluminum hydride, and the like. For additional examples, seeR. Larock, Comprehensive Organic Transformations: A Guide to FunctionalGroup Preparations (1989), pp. 432-434, and M. Smith and J. March,March's Advanced Organic Chemistry, 5^(th) ed. (2001), pp. 1549-1550.

In an alternative synthetic approach, the fatty amine is made by firstreducing the metathesis-derived acid or ester derivative to give a fattyalcohol, followed by amination of the fatty alcohol. Themetathesis-derived acid or ester derivative is reduced to a fattyalcohol using a metal hydride reagent (sodium borohydride, lithiumaluminum hydride, or the like), catalytic hydrogenation, or otherwell-known techniques for generating the fatty alcohol (see, e.g., U.S.Pat. Nos. 2,865,968; 3,193,586; 5,124,491; 6,683,224; and 7,208,643, theteachings of which are incorporated herein by reference). Amination isthen preferably performed in a single step by reacting the fatty alcoholwith ammonia or a primary or secondary amine in the presence of anamination catalyst. Suitable amination catalysts are well known.Catalysts comprising copper, nickel, and/or alkaline earth metalcompounds are common. For suitable catalysts and processes foramination, see U.S. Pat. Nos. 5,696,294; 4,994,622; 4,594,455;4,409,399; and 3,497,555, the teachings of which are incorporated hereinby reference.

In a preferred aspect, the fatty amine is a fatty amidoamine made byreacting a metathesis-derived C₁₀-C₁₇ monounsaturated acid or its esterderivative with an aminoalkyl-substituted tertiary amine. This providesa product having tertiary amine functionality without the need to reducea fatty amide to a fatty amine with a strong reducing agent. Suitableaminoalkyl-substituted tertiary amines have a primary amino group at oneterminus, an alkylene group, and a tertiary amine group at the other endof the molecule. The alkylene group is preferably a C₂-C₆ linear orbranched diradical such as ethylene, propylene, butylene, or the like.Thus, suitable aminoalkyl-substituted tertiary amines include, forexample, N,N-dimethyl-1,2-ethanediamine, N,N-dimethyl-1,3-propanediamine(DMAPA), N,N-diethyl-1,3-propanediamine, N,N-dimethyl-1,4-butanediamine,and the like. DMAPA is particularly preferred. The primary amine groupexhibits good reactivity with the acid or ester derivative, while theterminal tertiary amine is preserved in the product and provides a sitefor quaternization.

The relative amounts of secondary amine or aminoalkyl-substitutedtertiary amine reacted with the ester or acid reactants depends on thedesired stoichiometry and is left to the skilled person's discretion. Ingeneral, enough of the secondary amine (or aminoalkyl-substitutedtertiary amine) is used to react with most or all of the available acidor ester groups, i.e., preferably greater than 90%, and more preferablygreater than 95%, of the available acid or ester groups.

The tertiary amine group of the fatty amine or fatty amidoamine isquaternized to give a quaternary ammonium composition (“quaternizedfatty amine” or “quaternized fatty amidoamine”). Suitable quaternizingmethods and reagents are well known in the art. Common reagents include,for example, alkyl halides (methyl chloride, methyl bromide), dialkylsulfates, carbonates, or phosphates (dimethyl sulfate, diethyl sulfate,dimethyl carbonate), benzyl chloride, acetyl chloride, ethylene oxide,and the like.

Some quaternized fatty amines have the formula:

R²(R³)N⁺(R¹)R⁴X⁻

wherein:

R¹ is —C₁₀H₁₈—R⁵ or —C₁₈H₃₄—N⁺(R²)(R³)R⁴X⁻; each of R² and R³ isindependently substituted or unsubstituted alkyl, aryl, alkenyl,oxyalkylene, or polyoxyalkylene; R⁴ is C₁-C₆ alkyl; X⁻ is a halide,bicarbonate, bisulfate, or alkyl sulfate; and R⁵ is hydrogen or C₁-C₇alkyl. Preferably, R¹ is —(CH₂)₈—CH═CHR⁵ or—(CH₂)₈—CH═CH—(CH₂)₈—N⁺(R²)(R³)R⁴X⁻.

Some quaternized fatty amidoamines have the formula:

R⁴(R³)(R²)N⁺(CH₂)_(n)NH(CO)R¹X⁻

wherein: R¹ is —C₉H₁₆—R⁵ or —C₁₆H₃₀—(CO)NH(CH₂)_(n)N⁺(R²)(R³)R⁴X⁻; eachof R² and R³ is independently substituted or unsubstituted alkyl, aryl,alkenyl, oxyalkylene, or polyoxyalkylene; R⁴ is C₁-C₆ alkyl; X⁻ is ahalide, bicarbonate, bisulfate, or alkyl sulfate; R⁵ is hydrogen orC₁-C₇ alkyl; and n=2 to 8. Preferably, R¹ is —(CH₂)₇—CH═CH—R⁵ or—(CH₂)₇—CH═CH—(CH₂)₇—(CO)NH(CH₂)_(n)N⁺(R²)(R³)R⁴X⁻.

Specific examples of C₁₀, C₁₂, C₁₄, and C₁₆-based quaternized fattyamines and fatty amidoamines appear below:

2. Imidazoline Quats

Suitable imidazolines (precursors to imidazoline quats) are made byreacting a metathesis-derived C₁₀-C₁₇ monounsaturated acid or its esterderivative with diethylene triamine (DETA), (2-aminoethyl)ethanolamine(AEEA), or an alkoxylated derivative thereof. DETA and AEEA can reactwith two equivalents of a C₁₀-C₁₇ monounsaturated acid or its esterderivative to give an imidazoline amide or ester, respectively, whichhave a tertiary nitrogen available for quaternization.

The starting ester is commonly heated with a tertiary amine catalyst(e.g., DABCO, 1,4-diazabicyclo[2.2.2]octane), and DETA or AEEA at 80° C.to 250° C. Additional DETA or AEEA is added to the reactor as needed.When the initial reaction is complete (as is usually indicated by nofurther distillate of an alcohol), an acid catalyst such asβ-toluenesulfonic acid is added, and the mixture is heated at elevatedtemperature (e.g., 150° C. to 300° C., preferably from 180° C. to 250°C.) to effect the desired ring closure. Preferably, two moles of C₁₀ toC₁₇ acid or ester derivative per mole of DETA or AEEA are used to enableproduction of an imidazoline.

Quaternization of the imidazolines is accomplished by warming them witha quaternizing agent such as an alkyl halide or dialkyl sulfate.Specific examples include dimethylsulfate, methyl chloride,epichlorohydrin, benzyl chloride, alkali metal chloroacetates, and thelike. Dimethyl sulfate is particularly preferred. The reaction isgenerally performed at a temperature within the range of 30° C. to 150°C., preferably from 65° C. to 100° C., or more preferably from 80° C. to90° C. The amount of quaternizing agent used is typically 0.8 to 1.2mole equivalents based on the tertiary nitrogen content. The reaction isdeemed complete when the free amine value is in the desired range asdetermined by perchloric acid titration or other suitable analyticalmethod. Suitable methods for quaternizing imidazolines are disclosed inU.S. Pat. Nos. 5,750,492; 5,783,534; 5,939,059; and 6,004,913, theteachings of which are incorporated herein by reference.

Examples of suitable C₁₀, C₁₂, C₁₄, and C₁₆-based quaternizedimidazolines:

3. Esteramine Quats

Suitable esteramines (precursors to the esteramine quats) are made byreacting a metathesis-derived C₁₀-C₁₇ monounsaturated acid or its esterderivative with a tertiary alkanolamine.

Suitable tertiary alkanolamines have a tertiary amine group and from oneto three primary or secondary hydroxyl groups. In preferredalkanolamines, the tertiary nitrogen is attached to zero, one, or twoC₁-C₁₀ alkyl groups, preferably C₁-C₄ alkyl groups, and from one tothree hydroxyalkyl groups having from 2 to 4 carbons each, where thetotal number of alkyl and hydroxyalkyl groups is three. Suitablealkanolamines are well known and commercially available from BASF, DowChemical and other suppliers.

They include, for example, triethanolamine, N-methyldiethanolamine,N,N-dimethylethanolamine, N,N-dimethylpropanolamine,N,N-dimethylisopropanolamine, N-methyldiisopropanolamine,N,N-diethylethanolamine, triisopropanolamine, and the like, and mixturesthereof. Particularly preferred alkanolamines are triethanolamine,N-methyldiethanolamine, and N,N-dimethylethanolamine, which areeconomical and readily available.

Suitable alkanolamines include alkoxylated derivatives of the compoundsdescribed above. Thus, for example, the alkanolamine used to make theesteramine can be a reaction product of an alkanolamine with 0.1 to 20moles of ethylene oxide or propylene oxide per mole of —OH groups in thealkanolamine.

The esteramines are made using a well-known process that provides aunique product mixture because of the unconventional starting mixture ofacid or ester derivatives. The reactants are typically heated, with orwithout a catalyst under conditions effective to esterify ortransesterify the starting acid or ester with the tertiary alkanolamine.The reaction temperature is typically within the range of 80° C. to 300°C., preferably from 150° C. to 200° C., and more preferably from 165° C.to 180° C.

The relative amounts of alkanolamine and ester or acid reactants useddepend on the desired stoichiometry and is left to the skilled person'sdiscretion. Preferably, however, the equivalent ratio of acyl groups (inthe metathesis-derived acid or ester derivative) to hydroxyl groups (inthe tertiary alkanolamine) is within the range of 0.1 to 3, preferablyfrom 0.3 to 1. The ratio is frequently about 1, but lower acyl:hydroxylequivalent ratios are also common.

Some esteramines have the formula:

(R¹)_(3-m)—N—[(CH₂)_(n)—(CHCH₃)_(z)—O—CO—R²]_(m)

wherein:

R¹ is C₁-C₆ alkyl; R² is —C₉H₁₆—R³ or —C₁₆H₃₀—CO₂R⁴; R³ is hydrogen orC₁-C₇ alkyl; R⁴ is substituted or unsubstituted alkyl, aryl, alkenyl,oxyalkylene, polyoxyalkylene, glyceryl ester, or a mono- or divalentcation; m=1-3; n=1-4; z=0 or 1; and when z=0, n=2-4.

Preferably, R² is —(CH₂)₇—CH═CHR³ or —(CH₂)₇—CH═CH—(CH₂)₇—CO₂R⁴.

Esteramines are reacted with a quaternizing agent to give the esteraminequats according to well-known methods. Typically, the esteramine iswarmed with a quaternizing agent such as an alkyl halide or dialkylsulfate. Specific examples include dimethylsulfate, methyl chloride,epichlorohydrin, benzyl chloride, alkali metal chloroacetates, and thelike. Dimethyl sulfate and benzyl chloride are particularly preferred.The reaction is generally performed at a temperature within the range of30° C. to 150° C., preferably from 65° C. to 100° C., or more preferablyfrom 80° C. to 90° C. The amount of quaternizing agent used is typically0.8 to 1.0 mole equivalents based on the tertiary nitrogen content. Thereaction is deemed complete when the free amine value is in the desiredrange as determined by perchloric acid titration. Suitable methods forquaternizing the esteramines are disclosed in U.S. Pat. Nos. 5,750,492;5,783,534; 5,939,059; and 6,004,913, the teachings of which areincorporated herein by reference.

Examples of suitable C₁₀, C₁₂, C₁₄, and C₁₆-based quaternizedesteramines (“ester quats”):

II. Synergistic Surfactant Blend: Metathesis-Based Anionic Surfactant

Another synergistic surfactant blend of the invention comprises ametathesis-based anionic surfactant. This blend comprises a cationicsurfactant and an anionic surfactant comprising a sulfonated derivative.The sulfonated derivative is selected from fatty ester sulfonates, fattyacid sulfonates, sulfoestolides, fatty amide sulfonates, sulfonatedfatty ester alkoxylates, imidazoline quat sulfonates, sulfonatedamidoamine oxides, and sulfonated amidoamine betaines. The sulfonatedderivative is made from a metathesis-derived C₁₀-C₁₇ monounsaturatedacid, octadecene-1,18-dioic acid, or their ester derivatives.

A. The Cationic Surfactant

Suitable cationic surfactants include fatty amine salts (includingdiamine or polyamine salts), quaternary ammonium salts, salts of fattyamine ethoxylates, quaternized fatty amine ethoxylates, and the like,and mixtures thereof. Useful cationic surfactants are disclosed inMcCutcheon's Detergents &Emulsifiers (M.C. Publishing, N. American Ed.,1993); Schwartz et al., Surface Active Agents, Their Chemistry andTechnology (New York: Interscience, 1949) and in U.S. Pat. Nos.3,155,591; 3,929,678; 3,959,461; 4,275,055; and 4,387,090. Suitableanions include halogen, sulfate, methosulfate, ethosulfate, tosylate,acetate, phosphate, nitrate, sulfonate, carboxylate, and the like.

Suitable quaternary ammonium salts include mono-long chainalkyl-tri-short chain alkyl ammonium halides, wherein the long chainalkyl group has from about 8 to about 22 carbon atoms and is derivedfrom long-chain fatty acids, and wherein the short chain alkyl groupscan be the same or different but preferably are independently methyl orethyl. Specific examples include cetyl trimethyl ammonium chloride andlauryl trimethyl ammonium chloride. Preferred cationic surfactantsinclude octyltrimethyl ammonium chloride, decyltrimethyl ammoniumchloride, dodecyltrimethyl ammonium bromide, dodecyltrimethyl ammoniumchloride, and the like. Cetrimonium chloride (hexadecyltrimethylammoniumchloride) supplied as Ammonyx® Cetac 30, product of Stepan Company) is apreferred example.

Salts of primary, secondary and tertiary fatty amines are also suitablecationic surfactants. The alkyl groups of such amine salts preferablyhave from about 12 to about 22 carbon atoms, and may be substituted orunsubstituted. Secondary and tertiary amine salts are preferred, andtertiary amine salts are particularly preferred. Suitable amine saltsinclude the halogen, acetate, phosphate, nitrate, citrate, lactate andalkyl sulfate salts. Salts of, for example, stearamidopropyl dimethylamine, diethylaminoethyl stearamide, dimethyl stearamine, dimethylsoyamine, soyamine, myristyl amine, tridecylamine, ethyl stearylamine,N-tallowpropane diamine, ethoxylated stearylamine, stearylamine hydrogenchloride, soyamine chloride, stearylamine formate, N-tallowpropanediamine dichloride stearamidopropyl dimethylamine citrate, and the likeare useful herein.

Suitable cationic surfactants include imidazolines, imidazoliniums, andpyridiniums, and the like, such as, for example,2-heptadecyl-4,5-dihydro-1H-imidazol-1-ethanol,4,5-dihydro-1-(2-hydroxyethyl)-2-isoheptadecyl-1 phenylmethylimidazoliumchloride, and 1-[2-oxo-2-[[2-[(1-oxoctadecyl)oxy]ethyl]-amino]ethyl]pyridinium chloride. For more examples, see U.S. Pat. No. 6,528,070, theteachings of which are incorporated herein by reference. Other suitablecationic surfactants include quaternized esteramines or “ester quats,”and as disclosed in U.S. Pat. No. 5,939,059, the teachings of which areincorporated herein by reference. The cationic surfactant may be a DMAPAor other amidoamine-based quaternary ammonium material, includingdiamidoamine quats. It may also be a di- or poly-quaternary compound(e.g., a diester quat or a diamidoamine quat). Anti-microbial compounds,such as alkyldimethylbenzyl ammonium halides or their mixtures withother quaternary compounds, are also suitable cationic surfactants. Anexample is a mixture of an alkyl dimethylbenzyl ammonium chloride and analkyl dimethyl ethylbenzylammonium chloride, available commercially fromStepan Company as BTC® 2125M.

Many suitable cationic surfactants are commercially available fromStepan Company and are sold under the Ammonyx®, Accosoft®, Amphosol®,BTC®, Stepanquat®, and Stepantex® trademarks. For further examples ofsuitable cationic surfactants, see U.S. Pat. No. 6,528,070, theteachings of which are incorporated herein by reference.

B. The Metathesis-Derived Anionic Surfactant

The metathesis-derived anionic surfactant comprises a sulfonatedderivative selected from the group consisting of fatty ester sulfonates,fatty acid sulfonates, sulfoestolides, fatty amide sulfonates,sulfonated fatty ester alkoxylates, imidazoline quat sulfonates,sulfonated amidoamine oxides, and sulfonated amidoamine betaines. Thesulfonated derivative is made from a metathesis-derived C₁₀-C₁₇monounsaturated acid, octadecene-1,18-dioic acid, or their esterderivatives.

The metathesis-derived C₁₀-C₁₇ monounsaturated acid and its derivativesdescribed in Section I.B. (above) are also useful for makingmetathesis-derived anionic surfactants. Thus, for a description ofsuitable feedstocks for making the metathesis-based anionic surfactants,as well as suitable raw materials and metathesis catalysts, see SectionI.B. Some of the metathesis-derived sulfonated derivatives can be madefrom octadecene-1,18-dioic acid or its ester derivatives. The diacid isavailable from natural oil self-metathesis according to well-knownprocedures (see preparation of diesters C18-0 and Mix-0 below).

1. Fatty Acid Sulfonates and Fatty Ester Sulfonates

These sulfonates are made by reacting a metathesis-derived C₁₀-C₁₇monounsaturated acid, octadecene-1,18-dioic acid, or their esterderivatives with a sulfonating or sulfitating agent.

Sulfonation is performed using well-known methods, including reactingthe olefin with sulfur trioxide. Sulfonation may optionally be conductedusing an inert solvent. Non-limiting examples of suitable solventsinclude liquid SO₂, hydrocarbons, and halogenated hydrocarbons. In onecommercial approach, a falling film reactor is used to continuouslysulfonate the olefin using sulfur trioxide. Other sulfonating agents canbe used with or without use of a solvent (e.g., chlorosulfonic acid,fuming sulfuric acid), but sulfur trioxide is generally the mosteconomical. The sultones that are the immediate products of reactingolefins with SO₃, chlorosulfonic acid, and the like may be subsequentlysubjected to a hydrolysis reaction with aqueous caustic to affordmixtures of alkene sulfonates and hydroxyalkane sulfonates. Suitablemethods for sulfonating olefins are described in U.S. Pat. Nos.3,169,142; 4,148,821; and U.S. Pat. Appl. Publ. No. 2010/0282467, theteachings of which are incorporated herein by reference.

Sulfitation is accomplished by combining an olefin in water (and usuallya cosolvent such as isopropanol) with at least a molar equivalent of asulfitating agent using well-known methods. Suitable sulfitating agentsinclude, for example, sodium sulfite, sodium bisulfite, sodiummetabisulfite, or the like. Optionally, a catalyst or initiator isincluded, such as peroxides, iron, or other free-radical initiators.Typically, the reaction mixture is conducted at 15-100° C. until thereaction is reasonably complete. Suitable methods for sulfitatingolefins appear in U.S. Pat. Nos. 2,653,970; 4,087,457; 4,275,013, theteachings of which are incorporated herein by reference.

Sulfonation or sulfitation of the metathesis-derived C₁₀-C₁₇monounsaturated acid, octadecene-1,18-dioic acid, or their esterderivatives provides reaction products that include one or more ofalkanesulfonates, alkenesulfonates, sultones, hydroxy-substitutedalkanesulfonates. Mixtures of these reaction products are typical (see,e.g., sulfonates C10-1 and C12-1, in the examples below).

Some preferred alkanesulfonates have the structure:

XO₃S—[C_(n)H_(2n)CO₂R]

wherein X is H, an alkali metal, ammonium, or alkylammonium cation; R isX or C₁-C₁₀ alkyl or aryl; n=9-16; and the S atom is bonded to anycarbon on the C_(n)H_(2n) chain. Preferably, the S atom is bonded at theC9 or C10 position relative to the carbonyl carbon. Preferably, theC_(n)H_(2n) chain is linear. When n=9, the S atom is bonded to C₁₀.

Additional preferred alkanesulfonates have the structure:

(XO₃S)₂—[C_(n)H_(2n-1)CO₂R]

wherein X is H, an alkali metal, ammonium, or alkylammonium cation; R isX or C₁-C₁₀ alkyl or aryl; n=9-16; and the S atoms are bonded to anypair of adjacent carbons on the C_(n)H_(2n-1) chain. Preferably, the Satoms are bonded at the C9 and C10 positions relative to the carbonylcarbon. Preferably, the C_(n)H_(2n-1) chain is linear. When n=9, an Satom is bonded to C10.

Some preferred alkenesulfonates have the structure:

XO₃S—[C_(n)H_(2n-2)CO₂R]

wherein X is H, an alkali metal, ammonium, or alkylammonium cation; R isX or C₁-C₁₀ alkyl or aryl; n=9-16; and the S atom is bonded to anycarbon on the C_(n)H_(2n-2) chain. Preferably, the S atom is bonded atthe C9 or C10 position relative to the carbonyl carbon. In morepreferred alkenesulfonates, the S atom is bonded at the C9 or C10position and the unsaturation is allylic with respect to sulfur.Preferably, the C_(n)H_(2n-2) chain is linear. When n=9, the S atom isbonded to C₁₀.

Some preferred hydroxyalkanesulfonates have the structure:

XO₃S—[C_(n)H_(2n-1)CO₂R]—OH

wherein X is H, an alkali metal, ammonium, or alkylammonium cation; R isX or C₁-C₁₀ alkyl or aryl; n=9-16; the S atom is bonded to any carbon onthe C_(n)H_(2n-1) chain, and the OH group is bonded to a carbon that isα, β, or γ relative to the carbon that is substituted with the —SO₃Xgroup. Preferably, the S atom is bonded at the C9 or C10 positionrelative to the carbonyl carbon. Preferably, the C_(n)H_(2n-1) chain islinear. When n=9, the S atom is bonded to C₁₀.

Preferred sultones are β-, γ-, or δ-sultones, which have four, five, orsix-membered rings, respectively, that incorporate a —SO₂—O— groupwithin the ring. As the skilled person appreciates, the sultones aretypically intermediates that, through appropriate processing conditionssuch as treatment with aqueous alkali, may be converted tohydroxyalkanesulfonates and/or alkenesulfonates.

Some specific examples of C₁₀, C₁₂ and C₁₆-based sulfonate mixturesappear below:

2. Sulfoestolides

Suitable sulfonated derivatives include sulfo-estolides made by reactinga metathesis-derived C₁₀-C₁₇ monounsaturated acid oroctadecene-1,18-dioic acid with a sulfonating agent. Optionally, thesulfo-estolide is made by reacting the metathesis-derived C₁₀-C₁₇monounsaturated acid, octadecene-1,18-dioic acid, or their esterderivatives with a sulfonating agent in the presence of an additionalcarboxylic acid. The additional carboxylic acid can be saturated orunsaturated and branched or unbranched. In some instances, theadditional carboxylic acid is preferably a saturated C₆ to C₁₈carboxylic acid. Suitable sulfo-estolides have the structural moiety:

in which R is a linear or branched, saturated or unsaturated,substituted or unsubstituted alkyl radical and M is hydrogen or a monoor divalent cation (shown as monovalent above) such as sodium,potassium, calcium, trialkanolammonium, or the like.

Sulfonation converts some of the carbon-carbon double bonds in themetathesis-derived acid or ester reactant to sultones, particularlyβ-sultones. These are believed to undergo nucleophilic attack by acarboxylic oxygen to give a sulfo-estolide. The scheme below depicts apossible reaction pathway using a C₁₀ unsaturated fatty acid as thereactant:

As the skilled person will appreciate, the product mixture will be morecomplex than shown above, for example, when the starting material is amixture of different unsaturated acids and/or esters, or when thesulfonation is performed under conditions that promote isomerization ofthe carbon-carbon double bond.

The product mixture may comprise oligomers, for example dimers andtrimers that are formed by the ring-opening of β-sultone with carboxlicacids of sulfo-estolides. The degree of oligomerization is optionallycontrolled by adjusting the proportion of saturated and unsaturatedfatty acid components, as the saturated fatty acid serves as a chainterminator. For examples of reactions used to produce sulfo-estolides,see U.S. Pat. Nos. 7,879,790 and 7,666,828 and U.S. Pat. Appl. Publ. No.2010/0016198, the teachings of which are incorporated herein byreference.

Some sulfo-estolides have the structure:

XO₃S—[C_(n)H_(2n-1)CO₂R]—OCOR¹

wherein X is H, an alkali metal, ammonium, or alkylammonium cation; R isX or C₁-C₁₀ alkyl or aryl; n=9-16; R¹ is a C₈ to C₁₈ saturated ormonounsaturated group. The S atom and the —OCOR¹ group are bonded tovicinal carbons on the C_(n)H_(2n-1) chain. When n=9, the S atom ispreferably bonded at the C10 position relative to the carbonyl carbon.

Some specific examples of sulfo-estolides:

3. Fatty Amide Sulfonates

The fatty amides (precursors to the fatty amide sulfonates) are made byreacting a metathesis-derived C₁₀-C₁₇ monounsaturated acid,octadecene-1,18-dioic acid, or their ester derivatives with ammonia or aprimary or secondary amine.

Suitable primary or secondary amines have one or two hydrogens attachedto the amino group. The remaining groups are typically alkyl orsubstituted alkyl groups, preferably C₁-C₁₀ alkyl, more preferably C₁-C₄alkyl. Thus, suitable primary or secondary amines include ethylamine,isopropylamine, N,N-dimethylamine, N,N-diethylamine,N,N-diisopropylamine, and the like. In one preferred class of primaryand secondary amines, a N or O atom is bonded to a carbon that is betaor gamma to the N atom of the amine. In some preferred primary orsecondary amines, the nitrogen is attached to one C₁-C₁₀ alkyl group,preferably a C₁-C₄ alkyl group, and one hydroxyalkyl group having from 2to 4 carbons. In other preferred primary or secondary amines, thenitrogen is attached to a hydrogen and two hydroxyalkyl groups havingfrom 2 to 4 carbons each. Alkanolamines, which have an oxygen atom betato the amine nitrogen, are particularly preferred. Suitablealkanolamines are well known and commercially available from BASF, DowChemical and other suppliers. They include, for example, ethanolamine,propanolamine, isopropanolamine, diethanolamine, N-methylethanolamine,N-methylisopropanolamine, N-ethylethanolamine, and the like, andmixtures thereof. Particularly preferred alkanolamines are ethanolamine,diethanolamine, and N-methylethanolamine, which are economical andreadily available.

Suitable primary and secondary amines include alkoxylated derivatives ofthe compounds described above. Thus, for example, the amine used to makethe fatty amide can be an amine-terminated polyether comprising 0.1 to20 moles of ethylene oxide or propylene oxide per mole of —OH group inthe alkanolamine.

Some amides have the formula:

R¹CO—NR²R₃

where R¹ is R⁴—C₉H₁₆— or R⁵O₂C—C₁₆H₃₀—; R⁴ is hydrogen or C₁-C₇ alkyl;R⁵ is substituted or unsubstituted alkyl, aryl, alkenyl, oxyalkylene,polyoxyalkylene, glyceryl ester, or a mono- or divalent cation; and eachof R² and R³ is independently H, C₁-C₆ alkyl, or —CH₂CH₂OR⁶ where R⁶ isH or C₁-C₆ alkyl. Preferably, R¹ is R⁴CH═CH—(CH₂)₇— orR⁵O₂C—(CH₂)₇—CH═CH—(CH₂)₇—.

Some specific examples of C₁₀, C₁₂, C₁₄, and C₁₆-based fatty amidesappear below:

The corresponding fatty amide sulfonates are made by reacting theabove-mentioned fatty amides with a sulfonating or sulfitating agent,generally as previously described in Section II.B.1, above.

Exemplary fatty amide sulfonates:

4. Sulfonated Fatty Ester Alkoxylates

Suitable alkoxylated fatty esters (precursors to the sulfonated fattyester alkoxylates) comprise a reaction product of a metathesis-derivedC₁₀-C₁₇ monounsaturated acid, octadecene-1,18-dioic acid, or their esterderivatives with one or more alkylene oxides in the presence of aninsertion catalyst to give an alkoxylated fatty ester. Alternatively,the metathesis-derived starting material is reacted with a glycol etheror a glycol ether alkoxylate, optionally in the presence of anesterification or transesterification catalyst, to give the alkoxylatedfatty ester. In yet another alternative, the metathesis-derived startingmaterial is reacted with one or more alkylene oxides to give a fattyacid alkoxylate, followed by etherification of the fatty acidalkoxylate.

Preferably, the alkoxylated fatty ester composition comprises a productmade by reacting the metathesis-derived feedstock with one or morealkylene oxides in the presence of an insertion catalyst.

Suitable alkylene oxides are C₂-C₄ alkylene oxides, particularlyethylene oxide, propylene oxide, and butylene oxides. Ethylene oxide andpropylene oxide are preferred. Ethylene oxide is particularly preferred.Mixtures or combinations of different alkylene oxides can be used ifdesired to generate a random distribution or a block of alkylene oxideunits.

The selection of alkylene oxide(s) and the proportion used relative tothe amount of metathesis-derived acid or ester depends on the desiredperformance characteristics of the product and is within the skilledperson's discretion. Preferably, n, which is the average number ofoxyalkylene units in the alkoxylated fatty ester, is within the range of1 to 100.

Preferably, ethylene oxide units are incorporated to enhancehydrophilicity of the composition when compared with the startingmetathesis-derived acid or ester. When relatively low hydrophilicity isdesired, n typically ranges from 1 to 5 EO units. For intermediatehydrophilicity, n typically ranges from 5 to 15 EO units, and for higherhydrophilicity, n typically ranges from 15 to 50 EO units.

Suitable insertion catalysts are well known. They include, for example,modified or composite metal oxides, such as magnesium oxide modifiedwith aluminum, gallium, zirconium, lanthanum, or other transitionmetals, calcined hydrotalcites, calcined aluminum magnesium hydroxides,and the like. Composite oxide catalysts comprising magnesium andaluminum are preferred. Usually, the metathesis-derived fatty acid orester is reacted in the presence of the alkylene oxide(s) and insertioncatalyst and under predetermined temperature and pressure conditions,typically under nitrogen or other inert atmosphere, and the alkoxylatedproduct is then isolated and purified by known methods. For particularexamples of suitable insertion catalysts and process details for makingalkoxylated fatty esters by alkylene oxide insertion, see U.S. Pat. Nos.5,817,844, 6,184,400, and 6,504,061, the teachings of which areincorporated herein by reference. The reaction is considered completewhen the product gives satisfactory analysis. For example, in the ¹H NMRspectrum, the chemical shift of the methylene group located alpha to thecarbonyl can be used to differentiate unreacted starting material fromalkoxylated product.

Some inventive alkoxylated fatty esters have the formula:

R²—CO—O-(AO)_(n)—R¹

wherein

R¹ is C₁-C₄ alkyl; AO is C₂-C₄ oxyalkylene; R² is R³—C₉H₁₆— orR¹(AO)_(n)O—CO—C₁₆H₃₀—; R³ is hydrogen or C₁-C₇ alkyl; and n, which isthe average number of oxyalkylene units, has a value within the range of1 to 100. Preferably, R¹ is methyl. Preferably, AO is oxyethylene,oxypropylene, or combinations thereof, more preferably oxyethylene.Preferably, R² is R³—CH═CH—(CH₂)₇— or R⁴O—CO—(CH₂)₇—CH═CH—(CH₂)₇—.

In some preferred compositions, n has a value within the range of 0.5 to5 (also referred to herein as “low-EO” compositions). In other preferredcompositions, n has a value within the range of 5 to 15 (also referredto herein as “mid-EO” compositions). In other preferred compositions, nhas a value within the range of 15 to 50 (also referred to herein as“high-EO” compositions).

Some specific examples of C₁₀, C₁₂, C₁₄, and C₁₆-based alkoxylated fattyesters appear below (where n generally has a value within the range of 1to 100):

The corresponding sulfonated fatty ester alkoxylates are made byreacting the above-mentioned alkoxylated fatty esters with a sulfonatingor sulfitating agent, generally as previously described in SectionII.B.1, above.

Exemplary sulfonated or sulfitated products (where n generally has avalue within the range of 1 to 100):

5. Imidazoline Quat Sulfonates

The imidazoline quats (precursors to the imidazoline quat sulfonates)are made by reacting a metathesis-derived C₁₀-C₁₇ monounsaturated acid,octadecene-1,18-dioic acid, or their ester derivatives with AEEA orDETA, followed by quaternization, as is generally described above inSection I.B.2. The corresponding imidazoline quat sulfonates are made byreacting the above-mentioned imidazoline quats with a sulfonating orsulfitating agent, generally as previously described above in SectionII.B.1.

Exemplary imidazoline quat sulfonates:

6. Sulfonated Amidoamine Oxides

The amidoamines (precursors to the amidoamine oxides and sulfonatedamidoamine oxides) are made by reacting a metathesis-derived C₁₀-C₁₇monounsaturated acid, octadecene-1,18-dioic acid, or their esterderivatives with an aminoalkyl-substituted tertiary amine as previouslydescribed in Section I.B.1., above.

Oxidation is accomplished by reacting the fatty amidoamine with onoxidant such as hydrogen peroxide, air, ozone, organic hydroperoxides,or the like, to covert a tertiary amine group to an amine oxidefunctionality according to well-known methods (see March's AdvancedOrganic Chemistry, 5^(th) Ed. (2001), p. 1541 and U.S. Pat. No.3,494,924). An exemplary procedure for oxidizing a fatty amidoamine tothe corresponding oxide using hydrogen peroxide also appears below.

The corresponding amidoamine oxide sulfonates are made by reacting theabove-mentioned amidoamine oxides with a sulfonating or sulfitatingagent, generally as previously described above in Section II.B.1.

Examples of suitable C₁₀, C₁₂, and C₁₄-based amidoamine oxides:

Exemplary sulfonated amidoamine oxides:

7. Sulfonated Amidoamine Betaines

The amidoamines (precursors to the amidoamine betaines and sulfonatedamidoamine betaines) are made by reacting a metathesis-derived C₁₀-C₁₇monounsaturated acid, octadecene-1,18-dioic acid, or their esterderivatives with an aminoalkyl-substituted tertiary amine as previouslydescribed in Section I.B.1., above.

Suitable amidoamine betaines are made by reacting the fatty amidoaminewith an ω-haloalkylcarboxylic acid or alkali metal salt thereof (e.g.,sodium monochloroacetate or potassium monochloropropionate) in thepresence of a strong base according to well-known methods.

Some amidoamine betaines have the formula:

R⁴(R³)(R²)N⁺(CH₂)_(n)NH(CO)R¹

wherein:

R¹ is —C₉H₁₆—R⁵ or —C₁₆H₃₀—(CO)NH(CH₂)_(n)N⁺(R²)(R³)R⁴; each of R² andR³ is independently substituted or unsubstituted alkyl, aryl, alkenyl,oxyalkylene, or polyoxyalkylene; R⁴ is C₂-C₄ alkylene carboxylate; R⁵ ishydrogen or C₁-C₇ alkyl; and n=2 to 8. Preferably, R¹ is—(CH₂)₇—CH═CH—R⁵ or —(CH₂)₇—CH═CH—(CH₂)₇—(CO)NH(CH₂)_(n)N⁺(R²)(R³)R⁴.

Specific examples of C₁₀, C₁₂, C₁₄, and C₁₆-based amidoamine betainesappear below:

The corresponding amidoamine betaine sulfonates are made by reacting theabove-mentioned amidoamine betaines with a sulfonating or sulfitatingagent, generally as previously described above in Section II.B.1.

Exemplary sulfonated amidoamine betaines:

III. Synergy Determination

Blends of the invention exhibit synergy as evidenced by a negative βvalue or a reduced interfacial tension (IFT) when compared with anexpected IFT value calculated from the individual surfactant components.

Interfacial tension is measured by any suitable method. Conveniently,interfacial tension of the individual components and the blends aremeasured at 0.01% total surfactant actives (diluted in deionized water)at ambient temperature against soybean oil or light mineral oil using aKrüss DSA-20 pendant drop tensiometer. The expected IFT value for ablend is calculated based on ideal mixing (non-synergistic) using theactive component in each blend. The equation used is:

Expected IFT=X·IFT_(A)+(1−X)·IFT_(B)

where X is the actives % of Component A, IFT_(A) is the IFT of ComponentA, and IFT_(B) is the IFT of Component B.

If the measured IFT for a blend is less than the expected IFT, the blendis synergistic; if the measured IFT for a blend is greater than theexpected IFT, the blend is antagonistic.

Synergy can also be evaluated with respect to a blend's beta parameter(β), which can be calculated from the measured critical micelleconcentration. Suitable methods for calculating β have been describedpreviously (see, e.g., U.S. Pat. No. 5,360,571, the teachings of whichare incorporated herein by reference).

Conveniently, the critical micelle concentration of a blend is measuredat dilute concentrations in deionized water with pH adjusted to bewithin the range of 6 to 7. Critical micelle concentration generallyrefers to the minimum concentration of surfactant (in mg/L) needed tosupport micelle formation. The measurement can be performed, forinstance, using a Krüss K12 tensiometer at 25° C. Once the criticalmicelle concentration is measured, the value of β can be found from:

$\frac{X^{2}{\ln \left( {\alpha \; {C_{12}/{XC}_{1}}} \right)}}{\left( {1 - X} \right)^{2}{\ln \left\lbrack {\left( {1 - \alpha} \right){C_{12}/\left( {1 - X} \right)}C_{2}} \right\rbrack}} = 1$and$\beta = \frac{\ln \left( {\alpha \; {C_{12}/{XC}_{1}}} \right)}{\left( {1 - X} \right)^{2}}$

where X is the total mole fraction of Surfactant 1 in the mixedmicelles; α is the mole fraction of Surfactant 1 in solution; C₁, C₂,and C₁₂ are the critical micelle concentrations of Surfactant 1,Surfactant 2, and their mixture; and β is the interaction parameter.

A negative value of β indicates synergy, while a positive value of βindicates antagonism, and values close to zero indicate little or nosynergy.

Because the blends exhibit synergy, less surfactant is needed (at leastin theory) to accomplish a similar task compared with the use of theindividual components. Thus, there is an economic incentive to utilizesynergistic blends. Traditionally, however, precipitation issues haveprevented cationic-anionic surfactant blends from broad applicability(see Background section). The inventive blends, which have at least onecomponent that is metathesis-based, have improved solubility profilesand are less inclined to precipitate from solution, particularly upondilution with water to commonly used actives levels. Thus, it becomespractical to make a cationic-anionic blend and take advantage of thecombined synergy and good solubility.

The surfactant blends are useful for laundry detergents, dishdetergents, household or industrial cleaners, personal care products,agricultural products, building materials, oil recovery compositions,emulsion polymers, and other practical applications.

The following examples merely illustrate the invention. Those skilled inthe art will recognize many variations that are within the spirit of theinvention and scope of the claims.

Feedstock Syntheses Preparation of Methyl 9-Decenoate (“C10-0”) andMethyl 9-Dodecenoate (“C12-0”)

The metathesis procedures of U.S. Pat. Appl. Publ. No. 2011/0113679, theteachings of which are incorporated herein by reference, are used togenerate feedstocks C10-0 and C12-0.

Preparation of Dimethyl 9-Octadecene-1,18-dioate (“Mix-0” or “C18-0”)

Eight samples of methyl 9-dodecenoate (10.6 g each, see Table 2) arewarmed to 50° C. and degassed with argon for 30 min. A metathesiscatalyst([1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichlororuthenium(3-methyl-2-butenylidene)-(tricyclohexylphosphine),product of Material) is added to the methyl 9-dodecenoate (amountindicated in Table 2) and vacuum is applied to provide a pressure of <1mm Hg. The reaction mixture is allowed to self-metathesize for the timereported. Analysis by gas chromatography indicates that dimethyl9-octadecene-1,18-dioate is produced in the yields reported in Table A.“Mix-0” is an 80:20 trans-/cis-isomer mixture obtained from the reactionmixture. Crystallization provides the all-trans-isomer feed, “C18-0.”

TABLE A Self-Metathesis of Methyl 9-Dodecanoate Catalyst LoadingReaction C18-0 Sample (ppm mol/mol)* Time (h) (GC Area %) A 100 3 83.5 B50 3 82.5 C 25 3 83.0 D 10 3 66.2 E 15 4 90.0 F 13 4 89.9 G 10 4 81.1 H5 4 50.9 *ppm mol catalyst/mol methyl 9-dodecenoate

Preparation of Surfactants from Metathesis-Based Feedstocks C10-25: C10DMA Amide

A round-bottom flask is charged with methyl ester feedstock C10-0 (235g) and the mixture is degassed with nitrogen. Sodium methoxide (5 g of30% solution in methanol) is added via syringe and the mixture isstirred for 5 min. Dimethylamine (67 g) is slowly added via sub-surfacedip tube. After the addition, the mixture is heated to 60° C. and heldovernight. The amide, C10-25, is recovered via vacuum distillation (120°C., 20 mm Hg). Yield: 241.2 g (96.3%). Iodine value=128.9 g 12/100 gsample. ¹H NMR (CDCl₃), δ (ppm)=5.8 (CH₂═CH—); 4.9 (CH₂═CH—); 2.8-3.0(—C(O)—N(CH₃)₂); 2.25 (—CH₂—C(O)—). Ester content (by ¹H NMR): 0.54%.

C12-25: C12 DMA Amide

A round-bottom flask is charged with methyl ester C12-0 (900 g) and thefeedstock is degassed with nitrogen at 60° C. Sodium methoxide (30 g of30% solution in methanol) is added via syringe and the mixture isstirred for 5 min. Vacuum is then applied and the reaction vesselsealed. Dimethylamine (200 g) is slowly added via sub-surface dip tubeagainst the static vacuum. After the addition, the remaining vacuum isreleased with nitrogen, and the mixture is heated to 70° C. for 1 h. Themixture is heated to 80° C., DMA is sparged through the liquid for 2 h,and the mixture is then heated to 90° C. for 1 h. The sparge is stopped,and the reaction is cooled to 75° C. Full vacuum is applied and held for0.5 h. The vacuum is released, and 50% H₂SO₄ (16.3 g) and deionizedwater (200 mL) are added to quench the catalyst. The organic layer iswashed with deionized water (2×300 mL, then 1×150 mL) and then 20% brinesolution (50 mL). The organic layer is concentrated (full vacuum, 75°C.) and vacuum distilled (pot: 140-150° C.) to isolate amide C12-25.Iodine value: 112.8 g I₂/100 g sample; % moisture: 65 ppm. ¹H NMR(CDCl₃), δ (ppm): 5.35 (—CH═CH—); 2.8-3.0 (—C(O)—N(CH₃)₂; 2.25(—CH₂—C(O)—).

C10-38: C10 Amine

Amide C10-25 (475 g) is slowly added over 3 h to a stirring THF slurryof LiAlH₄ (59.4 g) under nitrogen while maintaining the temperature at11-15° C. The mixture warms to room temperature and stirs overnight. Themixture is chilled in an ice bath, and water (60 g) is added cautiously,followed by 15% aq. NaOH solution (60 g) and then additional water (180g) is added. The mixture warms to room temperature and is stirred for 1h. The mixture is filtered, and the filter cake is washed with THF. Thefiltrates are combined and concentrated. NMR analysis of the crudeproduct indicates that it contains approximately 16% 9-decen-1-ol, aside-product formed during the reduction of the amide. In order tosequester the alcohol, phthalic anhydride is to be added, thus formingthe half-ester/acid. The product mixture is heated to 60° C. andphthalic anhydride (57.5 g) is added in portions. NMR analysis of themixture shows complete consumption of the alcohol, and the mixture isvacuum distilled to isolate C10-38. Amine value: 298.0 mg KOH/g; iodinevalue: 143.15 g 12/100 g sample; % moisture: 0.02%. ¹H NMR (CDCl₃), δ(ppm): 5.8 (CH₂═CH—); 4.9 (CH₂═CH—); 3.7 (—CH₂—N(CH₃)₂).

C12-26: C12 Amine

The procedure used to make C10-38 is generally followed with amideC12-25 (620 g) and LiAlH₄ (67.8 g). When the reaction is complete, water(68 g) and 15% aq. NaOH solution (68 g) and water (204 g) are used toquench the reaction. After the usual filtration and concentration steps,NMR analysis of the crude product shows approximately 16% 9-dodecen-1-olto be present. And phthalic anhydride (30 g) is added in order tosequester the alcohol. The mixture is then vacuum distilled to giveC12-26. Amine value: 258.1 mg KOH/g sample; iodine value: 120.0 g 12/100g sample. ¹H NMR (CDCl₃), δ: 5.35 (—CH═CH—); 2.2 (—CH₂—N(CH₃)₂).

C10-17: C10 DMAPA Amide

A round-bottom flask is charged with methyl ester C10-0 (500 g), DMAPA(331 g), and sodium methoxide/MeOH solution (0.5 wt. % sodium methoxidebased on the amount of methyl ester). The contents are heated slowly to140° C. and held for 6 h. The reaction mixture is vacuum stripped (110°C. to 150° C.). After cooling to room temperature, the product, C10-17,is analyzed. Amine value: 224.1 mg KOH/g; iodine value: 102.6 g 12/100 gsample; titratable amines: 99.94%. ¹H NMR (CDCl₃), δ (ppm): 5.75(CH₂═CH—); 4.9 (CH₂═CH—); 3.3 (—C(O)—NH—CH₂—); 2.15 (—N(CH₃)₂).

C12-17: C12 DMAPA Amide

A round-bottom flask is charged with methyl 9-dodecenoate (“C12-0,” 670g). The mixture is stirred mechanically, and DMAPA (387 g) is added. ADean-Stark trap is fitted to the reactor, and sodium methoxide (30 wt. %solution, 11.2 g) is added. The temperature is raised to 130° C. over1.5 h, and methanol is collected. After 100 g of distillate isrecovered, the temperature is raised to 140° C. and held for 3 h. ¹H NMRshows complete reaction. The mixture is cooled to room temperatureovernight. The mixture is then heated to 110° C. and DMAPA is recoveredunder vacuum. The temperature is slowly raised to 150° C. over 1.5 h andheld at 150° C. for 1 h. The product, amidoamine C12-17, is cooled toroom temperature. Amine value: 202.1 mg KOH/g; iodine value: 89.5 g12/100 g sample; free DMAPA: 0.43%; titratable amines; 100.3%. ¹H NMR(CDCl₃), δ: 5.4 (—CH═CH—); 3.3 (—C(O)—NH—CH₂—); 2.2 (—N(CH₃)₂).

C10-42: C10 Amine DMS Quat

Amine C10-38 (90.1 g) and isopropyl alcohol (50 g) are charged to aflask under nitrogen, and the stirred mixture is warmed to 60° C.Dimethyl sulfate (59.23 g) is added dropwise with air cooling tomaintain a reaction temperature of 60-70° C. Additional dimethyl sulfate(0.4 g) is added to ensure full conversion. The mixture is held at 70°C. for 3 h, then at 85° C. for 1 h. On cooling, C10-42 is analyzed: pH:9.15 (1% in 9:1 IPA/water); free amine: 0.057 meq/g; moisture: 0.05 wt.%; IPA: 24.4 wt. %.

C10-40: C10 Benzyl Quat

A flask equipped with a condenser and nitrogen inlet is charged withC10-38 (86.56 g) and methanol (30 g). The mixture is warmed to 80° C.and benzyl chloride (56.37 g) is added. The temperature is raised to 82°C. for 1 h. On cooling, C10-40 is analyzed: pH: 8.6 (1% in 9:1IPA/water); methanol: 17.5 wt. %; iodine value: 67.37; free amine: 0.065meq/g; tertiary amine: 0.0169 meq/g; active alkyl quat: 2.645 meq/g.

C12-45: C12 Amine DMS Quat

A flask equipped with nitrogen inlet is charged with amine C12-26 (95.5g), and the contents are warmed to 60° C. Dimethyl sulfate (54.28 g) isadded dropwise. The mixture is cooled to maintain a temperature from65-70° C. During the addition, a precipitate forms, and isopropylalcohol (26.4 g) is added. The mixture is stirred at 70° C. for 3 h.Additional dimethyl sulfate (0.55 g) is added to ensure a completeconversion, and the mixture is stirred at 70° C. for 3 h, then at 85° C.for 1 h. The product, C12-45, is analyzed: pH: 6.36 (1% in 9:1IPA/water); free amine: 0.040 meq/g; moisture: 0.4 wt. %; IPA: 11.6 wt.%.

C10-18: C10 DMAPA Quat

A flask equipped with condenser and nitrogen inlet is charged withamidoamine C10-17 (151.3 g). After warming to 80° C., dimethyl sulfate(68.38 g) is added dropwise. The temperature is raised to 85° C. and themixture is stirred for 2 h. Isopropyl alcohol (23.45 g) is added, andthe mixture stirs for 1 h. The product, C10-18, is analyzed: IPA: 7.72wt. %; pH: 8.41 (1% in 9:1 IPA/water); iodine value: 56.8; tertiaryamine: 0.020 meq/g; moisture: 1.7 wt. %; quaternary actives: 91.2 wt. %.

C10-19: C10 DMAPA Quat Sulfonate

Methyl quat C10-18 (98.30 g) and water (216.3 g) are charged to around-bottom flask equipped with stir bar, condenser, and thermocouple.The mixture is heated at 80° C. until homogeneous. Sodium metabisulfite(Na₂S₂O₅; 23.49 g, 1.03 eq. NaHSO₃) is added, and the mixture is held at80° C. overnight. ¹H NMR (D₂O) shows 50% conversion to the sulfitatedproduct. The mixture is held at 80° C. for 48 h and then reanalyzed;there are no significant changes. Sulfur dioxide is bubbled through themixture, which is then held at 80° C. overnight, but there are still nosignificant changes in the NMR spectrum. The reaction stirs at roomtemperature over the weekend. The pH is adjusted to 6.6 and the mixtureis heated at 80° C. overnight. NMR analysis shows that olefin peaks havediminished. The pH has dropped to 3 and is adjusted with caustic to 7.After heating for another 24 h, NMR analysis shows no more changes, with4-5% olefin remaining. Additional sodium metabisulfite (0.91 g, 0.04 eq.NaHSO₃) is added, and the reaction mixture is heated overnight. The ¹HNMR spectrum indicates complete conversion to the desired quatsulfonate, C10-19. Analysis shows: moisture: 60.1%; Na₂SO₄: 1.93%.

C10-20: C10 DMAPA AO

A round-bottom flask is charged with amidoamine C10-17 (162.6 g), water(267 g), and Hamp-Ex 80 (0.5 g). The mixture is heated to 50° C. undernitrogen and several small pieces of dry ice are added. Hydrogenperoxide (35 wt. % aqueous solution, 64.5 g) is added dropwise whilekeeping the temperature less than 75° C. After completing the H₂O₂addition, the mixture is maintained at 70° C. for 7 h. Peroxide papertest indicates <0.5% residual H₂O₂. The mixture is heated for 3 h at 75°C. and then cooled to room temperature to give amine oxide C10-20 inwater. The product comprises (by titration): 35.2% amine oxide; 0.85%free amine.

C10-21: C10 DMAPA AO Sulfonate

A round-bottom flask equipped with stir bar, condenser, and thermocoupleis charged with amine oxide C10-20 (212.4 g, 36.8% solids) and sodiummetabisulfite (Na₂S₂O₅; 28.09 g, 1.03 eq. NaHSO₃), and this mixture isstirred until homogeneous. The solution is heated to 80° C. and the pHis adjusted to 7.5 with SO₂ gas. After 30 min., the pH is adjusted againwith SO₂ to 7.5. After 1 h, the pH is adjusted a third time with SO₂ andis then heated at 80° C. overnight. After 16 h, ¹H NMR analysis (D₂O)indicates a complete reaction. The signal for the amine oxide methylgroup had shifted to 2.6 ppm (from 3.1 ppm in the starting material),indicating conversion of amine oxide to sulfitoamine. Sodium hydroxide(5.46 g, 0.2 eq.) is added to hydrolyze the sulfitoamine and the mixtureis heated at 80° C. overnight. After 16 h, ¹H NMR analysis indicatesthat the amine methyl signal has shifted to 2.2 ppm, indicatinghydrolysis of sulfitoamine to the corresponding amine. The mixture iscooled to 50° C. and the pH is adjusted from 10.1 to 8.3 by adding dryice. Hydrogen peroxide (28.43 g, 1.02 eq.) is added dropwise,maintaining the reaction temperature below 70° C. The mixture ismaintained at 70° C. for 16 h. The mixture is cooled to providesulfonate C10-21 as an aqueous solution. Analysis by ¹H NMR (D₂O)confirms formation of the amine oxide sulfonate, based appearance of theN(CH₃)₂ at 3.2 ppm, which matches up well with the N(CH₃)₂ in thestarting amine oxide, and a new signal at 2.7 ppm corresponding to theprotons adjacent to the sulfonate group (—CH₂SO₃Na).

C12-18: C12 DMAPA Quat

A flask equipped with condenser and nitrogen inlet is charged withamidoamine C12-17 (155.8 g), which is warmed to 80° C. Dimethyl sulfate(68.38 g) is added dropwise. The reaction temperature is raised to 85°C. and held for 1 h, then to 95° C. for 3 h. Isopropyl alcohol (24.9 g)is added, and the mixture stirs for 1 h. Analysis of the quat product,C12-18, shows: IPA: 8.9 wt. %; iodine value: 53.95; pH: 8.07 (1% in 9:1IPA/water); moisture: 0.6 wt. %.

MIX-26: C18 DiDMAPA Amide (80% trans, 20% cis)

Dimethyl ester C18-0 (824.3 g), DMAPA (519.5 g), and sodium methoxidesolution (2.4 wt. % NaOMe based on methyl ester) are heated slowly to140° C. and held for several hours. A subsurface nitrogen sparge isutilized at the end to facilitate the removal of methanol. Thetemperature is reduced to 100° C., and the contents are vacuum stripped.A solution made from deionized water (1.0 L) and 50% H₂SO₄ (11 g) isadded slowly to the molten reaction product. The mixture cools, and thepasty solids are isolated by filtration. The solids are washed withdeionized water, and the filtrate is extracted with chloroform (2×250mL). The chloroform extracts are concentrated, and the resulting yellowoil is identified as the cis-enriched product by ¹H NMR. The yellow oilis redissolved in CHCl₃, filtered through silica, and combined with thepasty solids. Additional CHCl₃ (100 mL) is added to the contents, andthe mixture is swirled on a rotary evaporator at 70° C. untilhomogeneous. Vacuum is applied, and the CHCl₃ is removed, followed bywater. Evaporation is discontinued when the product remains a solid at98° C. The cooled product, Mix-26, is analyzed: amine value: 229.1 mgKOH/g sample; free DMAPA: 0.08%; moisture: 0.09%; total alkalinity: 4.08meq/g. ¹H NMR (CDCl₃), δ (ppm)=5.3 (—CH═CH—); 3.25 (—C(O)—NH—CH₂—); 2.2(—N(CH₃)₂). ¹³C NMR (CDCl₃), δ (ppm)=130 (trans —CH═CH—); 129.5 (cis,—CH═CH—). Product ratio: 79.3% trans, 20.7% cis.

MIX-27: C18 DiDMAPA DiQuat (80:20 Trans-/Cis-)

A flask equipped with condenser and nitrogen inlet is charged withdiamide Mix-26 (157.3 g), which is warmed to 80° C. Dimethyl sulfate(68.38 g) is added dropwise. The reaction temperature is raised to 85°C. and the mixture is stirred for 2 h. Isopropyl alcohol (23.45 g) isadded, and the mixture stirs for 1 h. The diquat product, Mix-27, isanalyzed: IPA: 7.72 wt. %; pH: 8.41 (1% in 9:1 IPA/water); iodine value:56.76; tertiary amine: 0.020 meq/g; moisture: 1.7 wt. %; quaternaryactives: 91.2 wt. %.

C10-1: C10 Sulfonate

In a batch reactor maintained at 20° C. under a nitrogen flow (2L/min.), methyl decenoate (106.7 g, 0.58 mol) is added to methylenechloride (100 mL). Sulfur trioxide (46.1 g, 0.58 mol) is evaporated over30 min. via a 140° C. flash-pot and is bubbled through the reactor usingthe nitrogen stream. The addition rate of SO₃ is adjusted to keep thereaction temperature at or below 35° C. At the end of the addition, thereaction mixture is maintained for an additional 5 min. and the mixtureis then concentrated under vacuum. The acid product is then digested for1 h at 50° C. Methanol (7.5 g) is added to the acid (150 g), and thesolution is heated to 65° C. for 1 h. The mixture is cooled to 0° C.,and a solution prepared from 50% aqueous NaOH (16.48 g) and water (142.6g) is slowly added. When the addition is complete, the pH is about 1.5.Additional 50% aq. NaOH solution (4.2 g) is added to adjust the pH toabout 7. The mixture is heated to 85° C. while monitoring pH. The pH iskept between 5 and 7 by adding more 50% aq. NaOH. The stirred solutionis heated at 85° C. for a total of 8 h under a nitrogen purge to removemethanol and completely hydrolyze sultones. The resulting product(“C10-1”) is a mixture that includes an alkenesulfonate and ahydroxyalkane sulfonate. Moisture: 46.7 wt. %; sodium sulfate: 0.27 wt.%.

C12-1: C12 Sulfonate

C12-1 is synthesized in a manner similar to C10-1 using C12-0 (106.7 g,0.579 mol), methylene chloride (100 mL), and sulfur trioxide (46.1 g,0.575 mol). Digestion is carried out for 1 h at 65° C. Methanol (7.7 g)is added, and the mixture is warmed to 65° C. for 1 h. The acid isneutralized at 0° C. using aqueous sodium hydroxide (20.3 g of 50% aq.NaOH in 141.6 g of water). Hydrolysis is carried out at 85° C. untildetermined complete by ¹H NMR. The pH is maintained between 5-7 withfurther additions of 50% NaOH (aq). After the hydrolysis, a materialfound to be the starting methyl ester oils out of solution and forms asmall layer on top of the neutralized material. The oil layer is removedand the aqueous layer is analyzed. ¹H NMR data supports the proposedcomposition. Moisture: 47.1 wt. %; pH: 8.58 (1% in 9:1 IPA/water);sodium sulfate: 0.52 wt. %; unsulfonated matter: 2.05 wt. %; methanol:0.53 wt. %.

C10-36: C10 Fatty Acid

Methyl ester C10-0 (390.2 g) is charged to a round-bottom flask equippedwith an overhead stirrer. After warming to 70° C., a mixture of KOH inglycerol (16% KOH, 523 g) is added. The mixture is warmed to 100° C. andmore solid KOH (35.1 g) is added. The mixture stirs for 17 h. Gaschromatography shows ˜94% conversion to the free fatty acid. More solidKOH (10 g) is added, and the mixture stirs at 100° C. for 4 h.Conversion by GC is now >97%. The mixture stirs at 100° C. for another 4h and then cools to 80° C. Water (400 mL) and 30% aq. H₂SO₄ (500 mL) areadded. The mixture stirs at 80° C. for ˜1 h. The layers are separated,and the aqueous layer is removed. More water (500 mL) is added, and themixture is again heated to 80° C. with stirring for 30 min. The layersare again separated, and the aqueous phase is discarded. The washingprocess (with 500 mL of water) is repeated two more times. The resultingfree fatty acid, C10-36, is stripped under vacuum (80° C., 2 h) and isthereafter used without further purification. Yield: 357 g. ¹H NMRresults are consistent with the proposed structure. Moisture: 315 ppm.

C10-6: C10 DMEA Ester

Fatty acid C10-36 (153.7 g, 0.890 mol) and N,N-dimethylethanolamine(142.7 g, 1.60 mol) are charged to a flask equipped with heating mantle,temperature controller, mechanical agitator, nitrogen sparge, five-plateOldershaw column, and condenser. The mixture is gradually heated to 180°C. while the overhead distillate temperature is kept below 105° C. Afterthe reaction mixture temperature reaches 180° C., it is held at thistemperature overnight. Free fatty acid content by ¹H NMR: 5%(essentially complete). The mixture is cooled to 90° C. and the column,condenser, and nitrogen sparge are removed. Vacuum is applied inincrements to 20 mm Hg over 1 h, held at held at 20 mm Hg for 0.5 h,then improved to full vacuum for 1.5 h. The esteramine product, C10-6,has an unreacted dimethylethanolamine value of 0.41%. Purity isconfirmed by a satisfactory ¹H NMR spectrum.

C10-7: C10 DMEA Ester Quat

Esteramine C10-6 (98.9 g) and isopropyl alcohol (26.2 g) are charged toa round-bottom flask equipped with a reflux condenser,thermocouple/heating mantle, and nitrogen inlet. The sample is heated to65° C. Dimethyl sulfate (49.6 g) is added dropwise via an additionfunnel. Temperature is kept at or below 70° C. After the DMS is added,the temperature is increased to 70° C. and stirred for 3 h. The reactionis considered complete, as the perchloric acid titration (PAT) valueindicates <2% quaternizable amine remaining based on the original PATvalue of the esteramine. The reaction mixture is also heated at 80-85°C. for 1 h to ensure complete DMS removal; contents are also tested witha Drager apparatus for residual DMS.

C10-8: C10 Ethoxylated Fatty Acid Methyl Ester (“eFAME”)

C10-36 fatty acid (196.7 g, 1.117 mol) is charged to a round-bottomflask equipped with an overhead stirrer, Dean-Stark trap, refluxcondenser, thermocouple, heating mantle, and temperature controller.2-Methoxyethanol (170.0 g) and toluene (500 mL) are added. The mixtureis heated to 124° C. while β-toluenesulfonic acid (1.7 g) is added.Water of reaction begins to collect when the target temperature isreached. Heating continues for 4.5 h, and conversion to the eFAME (by ¹HNMR) is 96%. (Signals for the hydrogens alpha to the carbonyl are usedto determine degree of conversion.) The sample is stripped to removetoluene and excess 2-methoxyethanol. Residual toluene is removed bystirring at 150° C. under vacuum (1-5 mm Hg) with a low nitrogen sparge.

C10-29: C10 eFAME Sulfonate

A round-bottom flask equipped with stir bar, thermocouple, heatingmantle, temperature controller, and pH probe is charged with sodiumbisulfite (as Na₂S₂O₅, 27.5 g) and deionized water (120.0 g). The pH isadjusted to 6.6 by adding sodium hydroxide (11.6 g). The mixture isheated to 75° C. Isopropyl alcohol (20.0 g) is added, followed byt-butylperoxybenzoate (“TBB,” 50 μL, added by syringe). After 0.5 h,olefin C10-8 (64.3 g) is slowly added, followed by the remaining TBB(225 μL). The pH is kept at 7.0±0.1 with a low SO₂ sparge. After 16 h,¹H NMR in D₂O shows olefin peaks. The pH drifts to 8.8 and is adjusteddown to 6.8 with a low SO₂ sparge, and more isopropyl alcohol (40 mL) isadded to aid with solubility. After another 5 h, pH again drifts upwardand is adjusted to 6.8 with a low SO₂ sparge. After another 1.5 h, ¹HNMR indicates complete reaction.

C10-12: C10 DETA Amide

A round-bottom flask is charged with fatty acid C10-36 (310 g) and thefeedstock is degassed with nitrogen. Diethylenetriamine (“DETA,” 62.6 g)is added and the mixture is heated from 130° C. to 170° C. over 4 h andstirred (170 rpm) under a flow of nitrogen (175 mL/min.). After 18 h,titration reveals 0.097 meq/g of free fatty acid. The temperature isincreased to 200° C. for 4 h. Titration indicates 96% ring closure toform C10-12.

C10-13: C10 DETA Quat

A round-bottom flask is charged with imidazoline C10-12 (202.1 g), whichis degassed with nitrogen and heated to 75° C. Dimethyl sulfate (“DMS,”60.6 g) is added via addition funnel with cooling to keep the reactiontemperature at ˜80° C. After the DMS addition is complete, the mixtureis held at 80° C. for 1 h. Free amine (by perchloric acid titration):0.067 meq/g. Isopropyl alcohol (IPA) (13.9 g) is added, and the mixtureis heated to 85° C. for 1 h to destroy any unreacted DMS.

C10-32:C₁₀ UFA SLA

The procedure used to prepare C10-1 is generally followed with methylenechloride (100 mL) and sulfur trioxide (51.6 g, 0.644 mol), except thatfatty acid C10-36 (109.6 g, 0.644 mol) is used instead of methyl esterC10-0. During SO₃ addition, more methylene chloride (100 mL) is added toreduce viscosity. The acid is neutralized with water (151.0 g) followedby 50% aq. NaOH (41.69 g). Hydrolysis is carried out at 85° C. and pH ismaintained with additional 50% NaOH (aq) additions. ¹H NMR of thesulfo-estolide product, C10-32, supports the proposed structure.Analysis shows: pH: 5.25 (as is); moisture: 51.6 wt. %; sodium sulfate:0.51 wt. %; unsulfonated matter: 0.79 wt. %.

C18-1: C18 Sulfonate

The procedure used to synthesize C10-1 is generally followed using C18-0(125.8 g, 0.370 mol), methylene chloride (100 mL), and sulfur trioxide(30.4 g, 0.380 mol). Digestion is carried out for 1 h at 65° C. Methanol(7.24 g) is added, and the mixture is warmed to 65° C. for 1 h. The acidis neutralized at 0° C. using aqueous sodium hydroxide (a mixture of19.2 g of 50% NaOH and 107 g of water). Hydrolysis is carried out at 85°C. until ¹H NMR shows complete conversion. The pH is maintained between5-7 with further additions of 50% NaOH (aq). After the hydrolysis, asmall layer of oil, found to be starting methyl ester, forms on thesurface and is removed. ¹H NMR results supported the proposedcomposition for C18-1. Analysis shows: pH: 5.56 (1% in 9:1 IPA/water);moisture: 30.7 wt. %; sodium sulfate: 1.59 wt. %; unsulfonated matter:5.62 wt. %.

C10-26: C10 DMA Sulfonate

Sulfur trioxide (23.6 g) is added dropwise to unsaturated amide C10-25(48.6 g) in a vaporizer at a rate effective to maintain the reactiontemperature between 35-40° C. Initial fuming in the reactor headspace isminimal. About halfway through the SO₃ addition, the reaction productbecomes too viscous to stir adequately. The reactor is fitted with a dryice/acetone trap and the product is diluted with methylene chloride (50mL) to aid agitation. The reaction temperature is maintained between 20°C.-25° C. Additional methylene chloride (20 mL) is added during the SO₃addition to maintain fluidity. At the end of the addition, the reactoris purged with nitrogen for 5 min. Total addition time: 45 min. Theyellow-brown product (104.76 g) is transferred to a round-bottom flask,and solvent is removed under vacuum (40° C., 2 h). The resultingsulfonic acid is digested at 45° C. for 30 min. Yield: 71.4 g.

Aqueous sodium hydroxide (75 g of 10.7% solution) is added to the driedsulfonic acid. The pH is adjusted as necessary. Once dissolved, themixture is transferred to a flask equipped with mechanical stirring.Water (78.4 g) and aqueous NaOH (24.6 g of 50% solution) are added. Themixture is heated to 95° C. overnight, maintaining pH=7 with 50% aq.NaOH solution, and then cooled.

Preparation of Surfactant Blends

All of the surfactant blends tested are prepared at the designated molarratios without any pH adjustment. Dilutions are made using deionizedwater to the desired actives level. Actives amounts are wt. % unlessindicated otherwise. Appearances are reported at ambient temperature forsamples prepared within the last 24 h.

Interfacial tension (IFT) of all the individual components and theirblends is measured at a given % active against light mineral oil atambient temperature using a Kruss DSA-20 pendent drop tensiometer.

The critical micelle concentration (CMC) of a blend is measured at adiluted concentration in deionized water with pH adjusted to 6-7. Themeasurement is done at 25° C. using a Kruss K100 tensiometer. Thesynergy of the blends, indicated by the beta parameter, is calculatedbased on the CMC data using the equation,

β=[In(αA ₁₂ /XA ₁)]/(1−X)²

in which α is the mole fraction of the anionic surfactant in solution, Xis the mole fraction of the anionic surfactant in mixed micelles, A₁ isthe critical micelle concentration of the anionic surfactant, and A₁₂ isthe critical micelle concentration of the blend.

Surfactant Identification Table Commercial Product¹ % actives EW genericname Stepanol ® WA-Extra 29.2-29.4 302 sodium lauryl sulfate Ammonyx ®Cetac 30 29.4 320 cetrimonium chloride BTC ® 2125M 51.1 377myristylalkonium chloride + quaternium 14 Alpha-Step ® PC-48 37 338sodium methyl 2-sulfolaurate + disodium 2-sulfolaurate Stepanate ® SXS40.6 208 sodium xylene sulfonate Bio-Terge ® PAS-8S 40.5 242 sodiumoctane sulfonate Bio-Terge ® AS-40 39.3 315 sodium C14-C16 olefinsulfonate Stepanquat ® 1010-80 81.9 362 dodecyl dimethylammoniumchloride Inventive Surfactant % actives EW Generic Name C10-1 53.0 295C10 fatty ester sulfonate C10-7 86.8 368 C10 DMEA ester quat C10-13 86.9C10 DETA quat C10-19 34.6 485 C10 DMAPA quat sulfonate C10-21 47.1 376C10 DMAPA amine oxide sulfonate C10-26 40.1 301 C10 fatty amidesulfonate C10-29 45.8 332 C10 ethoxylated fatty methyl ester C10-40 82.0310 C10 fatty amine benzyl quat C12-1 52.4 323 C12 fatty ester sulfonate¹All products of Stepan Company.

TABLE 1 Metathesis-based Cationic Surfactant (C10-42) + AnionicSurfactants Sample C10-42 C10-1 Stepanol ® WA-Extra Type cationicanionic anionic Name C10 DMS quat C10 sulfonate sodium lauryl sulfateMetathesis-based? Y Y N IFT (0.1% actives) 42.0 47.1 7.8 C10-42:anionic(molar)  1:1 1:1 Total actives of blend, % 22.8 42.1 Appearance, neatclear liquid 2 layers Appearance, 1.0% clear liquid hazy liquidAppearance, 0.1% clear liquid slightly hazy liquid Calculated IFT (nosynergy) 44.5 25.1 Measured IFT (0.1% actives) 18.8  1.9 Synergy? Y YSolubility good fair-poor

TABLE 2 Metathesis-based Cationic Surfactant (Mix-27) + AnionicSurfactants Sample Mix-27 C10-1 Stepanol ® WA-Extra Type cationicanionic anionic Name C18 diDMAPA C10 sulfonate sodium lauryl sulfatediquat Metathesis-based? Y Y N IFT (0.1% actives) 47.1 7.8Mix-27:anionic (molar)  1:2 1:2 Total actives of blend, % 46.0 45.9Appearance, neat clear liquid clear liquid Appearance, 1.0% clear liquidhazy liquid Appearance, 0.1% clear liquid hazy liquid Calculated IFT (nosynergy) 35.3 18.0 Measured IFT (0.1% actives) 11.1  4.4 Synergy? Y YSolubility good-fair good-fair

As shown in Tables 1 and 2, combinations of a metathesis-based cationicsurfactant comprising a quaternized derivative, here a fatty amine quat(C10-42) or a fatty amidoamine quat (Mix-27), demonstrate synergy withanionic surfactants. The anionic surfactant may or may not bemetathesis-based. In addition to the reduction in IFT versus thecalculated value with no synergy, the blends demonstrate acceptable togood solubility, particularly at the 0.1 and 1.0% actives levelscommonly used in practical applications.

TABLE 3 Metathesis-based Anionic Surfactant (C10-1) + CationicSurfactants Sample C10-1 BTC ® 2125M Ammonyx ® Cetac 30 Type anioniccationic cationic Name C10 sulfonate myristylalkonium Cl + cetrimoniumCl quaternium 14 Metathesis-based? Y N N IFT (0.1% actives) 47.1 6.4 9.3C10-1:cationic (molar) 1:1 1:1 Total actives of blend, % 51.9 37.4Appearance, neat 2 layers clear liquid Appearance, 1.0% opaque liquidclear liquid Appearance, 0.1% sl. hazy liquid clear liquid CalculatedIFT 25.8 27.4 (no synergy) Measured IFT (0.1% actives)  0.09  2.6Synergy? Y+ Y Solubility good-fair good

TABLE 4 Metathesis-based Anionic Surfactant (C10-26) + CationicSurfactants Sample Ammonyx ® C10-26 BTC ® 2125M Cetac 30 C10-42 Typeanionic cationic cationic cationic Name C10 amide myristylalkonium Cl +cetrimonium Cl C10 DMS quat sulfonate quaternium 14 Metathesis-based? YN N Y IFT (0.1% actives) 12.5 6.4 9.3 42.0 C10-26:cationic (molar) 1:11:1  1:1 Total actives of blend, % 47.9  57.3 55.6 Appearance, neat 2layers clear liquid clear liquid Appearance, 1.0% clear liquid clearliquid hazy liquid Appearance, 0.1% clear liquid clear liquid clearliquid Calculated IFT 9.1 10.9 27.4 (no synergy) Measured IFT (0.1% 3.7 6.2 17.6 actives) Synergy? Y Y Y Solubility good-fair good good

TABLE 5 Metathesis-based Anionic Surfactant (C10-32) + CationicSurfactants Sample C10-32 C10-42 Ammonyx ® Cetac 30 Type anioniccationic cationic Name C10 sulfoestolide C10 DMS quat cetrimonium ClMetathesis-based? Y Y N IFT (0.1% actives) 25.9 42.0 9.3 C10-32:cationic(molar)  1:1 1:1 Total actives of blend, % 56.8 38.6 Appearance, neatclear liquid clear liquid Appearance, 1.0% hazy liquid clear liquidAppearance, 0.1% clear liquid clear liquid Calculated IFT 32.4 19.2 (nosynergy) Measured IFT (0.1% actives) 10.0  2.1 Synergy? Y Y Solubilitygood-fair good

TABLE 6 Metathesis-based Anionic Surfactant (C18-1) + CationicSurfactants Sample Ammonyx ® C18-1 C10-42 Cetac 30 Type anionic cationiccationic Name C18 sulfonate C10 DMS quat cetrimonium ClMetathesis-based? Y Y N IFT (0.1% actives) 11.7 42.0 9.3 C18-1:cationic(molar)  1:1 1:1 Total actives of 71.9 43.8 blend, % Appearance, neathazy liquid clear liquid Appearance, 1.0% hazy liquid hazy liquidAppearance, 0.1% clear liquid hazy liquid Calculated IFT 24.1 10.7 (nosynergy) Measured IFT 12.8  2.9 (0.1% actives) Synergy? Y Y Solubilityfair fair

The results in Tables 3-6 demonstrate the use of a metathesis-basedanionic surfactant comprising a sulfonated derivative with a cationicsurfactant. The sulfonated derivatives include sulfonated esters, amidesulfonates, and sulfoestolides. Based on the IFT data, each of theblends demonstrates synergy. The cationic surfactant may or may not bemetathesis-based.

In Tables 7-9 (below), blends made from metathesis-based cationicsurfactants and an anionic surfactant (Stepanol® WA-Extra, sodium laurelsulfate, “SLS”) are compared with blends made using SLS and a saturatedanalog of the metathesis-based cationic surfactant. The metathesis-basedcationic surfactants are principally monounsaturated materials. All ofthe blends in these tables are synergistic, as indicated by the largenegative values of β. However, the solubility profiles of blendscontaining the unsaturated materials (C10-18, C12-18, and C12-45) aregenerally more favorable, particularly for the C12 products. The resultssuggest that monounsaturation may provide advantages to formulators thatneed to ensure that actives will remain dissolved (and not precipitate)when combinations of anionic and cationic surfactants are used. Thesolubility advantages should allow formulators to take advantage ofsynergy in cationic/anionic surfactant blends by using less of the blendto achieve a desired reduction in surface tension, improvement incleaning, or other related properties.

TABLE 7 Blends of SLS and Metathesis-Based Cationic Surfactants: Effectof Unsaturation Monounsaturated C10 DMAPA quat (C10-18) Saturated analogSLS/Quat Appearance Appearance (molar) concentrate 0.2% actives 0.01%actives Beta concentrate 0.2% actives 0.01% actives Beta 1:0 clear clearclear clear clear clear 4:1 clear clear clear −3.9 viscous clear clear−6.8 2:1 2 layers viscoelastic clear −5.0 2 layers viscoelastic clear−7.9 1:1 clear hazy clear −7.0 clear hazy clear −8.3 1:2 clear gel clearclear −8.7 clear slightly hazy clear −11.8 1:4 clear gel hazy clear−10.9 clear clear clear −13.3 0:1 solid clear clear solid clear clearAll samples are liquid unless noted otherwise. SLS = Stepanol ® WA-Extra(sodium lauryl sulfate).

TABLE 8 Blends of SLS and Metathesis-Based Cationic Surfactants: Effectof Unsaturation Monounsaturated C12 DMAPA quat (C12-18) Saturated analogSLS/Quat Appearance Appearance (molar) concentrate 0.2% actives 0.01%actives Beta concentrate 0.2% actives 0.01% actives Beta 1:0 clear clearclear clear clear clear 4:1 clear clear clear −8.4 clear clear clear−8.4 2:1 hazy, viscous slightly hazy clear −10.9 hazy, viscous clearclear −10.1 1:1 hazy, viscous cloudy hazy −12.0 hazy, viscous cloudyhazy −8.2 1:2 clear slightly hazy clear −13.3 top hazy, slightly hazyhazy −12.7 bottom clear 1:4 clear clear slightly hazy −16.0 clear gelclear hazy −14.4 0:1 solid clear clear solid clear clear All samples areliquid unless noted otherwise. SLS = Stepanol ® WA-Extra (sodium laurylsulfate).

TABLE 9 Blends of SLS and Metathesis-Based Cationic Surfactants: Effectof Unsaturation Monounsaturated C12 DMA quat (C12-45) Saturated analogSLS/Quat Appearance Appearance (molar) concentrate 0.2% actives 0.01%actives Beta concentrate 0.2% actives 0.01% actives Beta 1:0 4:1 hazyslightly hazy clear −9.3 2 layers hazy almost clear −10.5 2:1 opaquehazy almost clear −11.0 2 layers hazy hazy −11.2 1:1 lamellar hazyalmost clear −14.1 paste hazy almost clear −13.8 1:2 2 layers hazy hazy−15.0 2 layers hazy hazy −14.2 1:4 clear slightly hazy clear −18.5 2layers hazy almost clear −19.1 0:1 All samples are liquid unless notedotherwise. SLS = Stepanol ® WA-Extra (sodium lauryl sulfate).

TABLE 10 Metathesis-based Anionic Surfactant (C10-1) in Combination withAmmonyx ® Cetac 30 (Cationic Surfactant): Solubility Evaluation Example# A1 A2* A3* A4* A5 A6 Ammonyx ® Cetac 5.0 5.0 5.0 5.0 5.0 18.9 30,active % C10-1, active % 2.5 5.0 18.9 Alpha-Step ® PC-48, 2.5 active %Stepanate ® SXS, 2.5 active % Bio-Terge ® PAS-8S, 2.5 active % Waterq.s. to 100 q.s. to 100 q.s. to 100 q.s. to 100 q.s. to 100 q.s. to 100pH 3.55 4.82 3.26 3.11 — — Total actives (%) 7.5 7.5 7.5 7.5 10.0 37.8Cat/an actives ratio 5/2.5 5/2.5 5/2.5 5/2.5 5/5 1/1 Cat/an molar ratio1.84 2.11 1.30 1.51 0.92 0.92 Appearance clear, low cloudy, low clear,cloudy, clear, low clear, low viscosity viscosity viscoelastic viscousviscosity viscosity Foam Volumes, mL Initial 340 320 150 140 — — 5 min310 300 150 140 — — Initial (+oil) 175 145 115 115 5 min (+oil) 175 145115 115 Sliming observed? N Y N Y — — *Comparative examples

As shown in Table 10, combination of a metathesis-based anionicsurfactant, C10-1, with a cationic surfactant (Ammonyx® Cetac 30)provides clear, low-viscosity liquids. This contrasts with traditionalanionic surfactants such as Bio-Terge® PAS-8S or Alpha-Step® PC-48,which often form a precipitate when combined with cationic surfactants.Stepanate® SXS acts as a counterion with Ammonyx® Cetac 30, giving avisoelastic liquid (Comparative Example A3), but that behavior is notseen with C10-1, where the mixture remains non-viscous.

The samples are further evaluated in a foaming test, with theC10-1/Cetac combination giving the best foaming, particularly with addedoil. The C10-1/Cetac blend also gives a reduced level of oiling out or“sliming” upon dilution to 0.2 wt. % actives in preparation for the foamtest.

Table 11 (below) shows a similar favorable solubility result whencombining metathesis-derived anionic surfactant C12-1 with Ammonyx®Cetac 30.

TABLE 11 Metathesis-based Anionic Surfactant (C12-1) + Ammonyx ® Cetac30 (Cationic Surfactant): Solubility Evaluation Example # B1 B2 C12-1,active % 5.0 10.0 Ammonyx ® Cetac 30, active % 5.0 2.0 Water q.s. to 100q.s. to 100 Total actives (%) 10 12 C12-1/Cetac 30 actives ratio 5/510/2 C12-1/Cetac 30 molar ratio 1/1  5/1 Appearance, neat clear clearAppearance, 0.2% actives clear hazy

Tables 12-14 illustrate the solubility performance of blends made from ametathesis-based cationic surfactant and a variety of anionicsurfactants. The metathesis-based cationic surfactants tested include anesteramine quat (C10-7, Table 12), an imidazoline quat (C10-13, Table13), and a fatty amine benzyl quat (C10-40, Table 14). As shown in Table12, blends of C10-7 with C10-29, a metathesis-based anionic surfactant,are synergistic (β=−5.62) and provide clear, low-viscosity liquids.Blends of C10-13 with the commercial anionic surfactant Stepanol® WAExtra SLS show acceptable compatibility when diluted to 0.2% actives(see Table 13). As shown in Table 14, blends of metathesis-based benzylquat C10-40 with commercial or metathesis-based anionic surfactantsprovide good solubility at 0.2% actives.

TABLE 12 Blend of Metathesis-based Cationic (C10-7) and AnionicSurfactants (C10-29) Synergy and Solubility Evaluation Active % MolesC10-7 (C10 DMEA Esterquat) 31.9 0.00274 C10-29 (C10 eFAME sulfonate)29.0 0.00275 Blend total active %, neat 60.9 Appearance, neat clear, lowviscosity Surface tension at CMC (mg/L) CMC (mol/L) CMC (mN/m)C10-7/C10-29 670 1.91 × 10⁻³ 34.8 equimolar blend C10-7 342.6 9.32 ×10⁻⁴ 41.1 C10-29 2244 6.75 × 10⁻³ 34.6 Beta, calculated −5.62 CMC =critical micelle concentration

TABLE 13 Blend of Metathesis-based Cationic Surfactant (C10-13) +Anionic Surfactant: Solubility Evaluation Active % C10-13 (C10 DETAQuat) 22.0 Stepanol ® WA-Extra SLS 22.0 Blend total active %, neat 44.0Appearance, neat flowable paste Appearance, 0.2% actives hazy,homogeneous liquid

TABLE 14 Metathesis-based Cationic Surfactant (C10-40) + AnionicSurfactants: Solubility Evaluation Example # D1 D2 D3 D4 C10-40 (C10Benzyl Quat), 6.70 8.77 8.31 8.94 active % Stepanol ® WA-Extra SLS,active % 26.8 Bio-Terge ® AS-40, active % 35.1 Alpha-Step ® PC-48,active % 33.3 C10-26 (C10 DMA sulfonate), 35.8 active % C10-40/othersurfactant (molar) 0.25 0.25 0.25 0.25 % Actives, total 33.5 43.9 41.644.7 Appearance, neat opaque, pearl-like clear liquid, low two phasesviscous, gel viscous liquid viscosity Appearance, 0.2% actives clearliquid clear liquid clear liquid clear liquid

We also found that certain metathesis-based surfactants provide goodsolubilities when combined with either an anionic or cationicsurfactant. For instance, Table 15 shows that a metathesis-based DMAPAquat sulfonate provides clear liquids when blended with a cationicsurfactant (Stepanquat® 1010-80) or anionic surfactants (Stepanol® WAExtra SLS or BTC® 2125M). Similar good solubilities are obtained whenmetathesis-based C10-21, a DMAPA amine oxide sulfonate, is blended withthe same commercial cationic or anionic surfactants (Table 16).

TABLE 15 Metathesis-based Surfactant (C10-19) + Anionic or CationicSurfactants: Solubility Evaluation Example # E1 E2 E3 C10-19 (C10 DMAPA26.3 19.9 22.7 Quat Sulfonate), active % Stepanquat ® 1010-80, 19.6active % Stepanol ® WA-Extra 12.4 SLS, active % BTC ® 2125M, active %17.6 molar ratio 1:1 1:1 1:1 % Actives, total 45.9 32.3 40.3 Appearance,neat clear liquid clear liquid clear liquid Appearance, 0.2% activesclear liquid clear liquid clear liquid

TABLE 16 Metathesis-based Surfactant (C10-21) + Anionic or CationicSurfactants: Solubility Evaluation Example # F1 F2 F3 C10-21 (C10 DMAPA30.3 24.5 20.5 AO Sulfonate), active % Stepanquat ® 1010-80, 29.1 active% BTC ® 2125M, active % 24.5 Stepanol ® WA-Extra 16.5 SLS, active %molar ratio 1:1 1:1 1:1 % Actives, total 59.5 49.0 37.0 Appearance, neathazy liquid clear liquid clear liquid Appearance, 0.2% actives hazyliquid clear liquid clear liquid

The preceding examples are meant only as illustrations. The followingclaims define the invention.

We claim:
 1. A surfactant blend comprising: (a) a cationic surfactant;and (b) an anionic surfactant comprising a sulfonated derivativeselected from the group consisting of: (i) sulfoestolides having thestructure:XO₃S—[C_(n)H_(2n-1)CO₂R]-OCOR¹ wherein X is H, an alkali metal,ammonium, or alkylammonium cation; R is X or C₁-C₁₀ alkyl or aryl;n=9-16; R¹ is a C₈ to C₁₈ saturated or monounsaturated group and the Satom and the —OCOR¹ group are bonded to vicinal carbons on theC_(n)H_(2n-1) chain; and (ii) fatty amide sulfonates produced bysulfonation of a fatty amide having the formula:R¹CO—NR²R₃ where R¹ is R⁴—C₉H₁₆— or R⁵O₂C—C₁₆H₃₀—; R⁴ is hydrogen orC₁-C₇ alkyl; R⁵ is substituted or unsubstituted alkyl, aryl, alkenyl,oxyalkylene, polyoxyalkylene, glyceryl ester, or a mono- or divalentcation; and each of R² and R³ is independently H, C₁-C₆ alkyl, or—CH₂CH₂OR⁶ where R⁶ is H or C₁-C₆ alkyl.
 2. The blend of claim 1 whereinthe cationic surfactant is a quaternized fatty amine or a quaternizedfatty amidoamine.
 3. The blend of claim 1 wherein the cationicsurfactant is cetrimonium chloride or a mixture of an alkyl dimethylbenzyl ammonium chloride and an alkyl dimethyl ethylbenzyl ammoniumchloride.
 4. The blend of claim 1 wherein the anionic surfactant is asulfoestolide having a structure selected from the group consisting of:


5. The blend of claim 1 wherein the anionic surfactant is a fatty amidesulfonate made by sulfonating a fatty amide having a structure selectedfrom the group consisting of:


6. The blend of claim 1 wherein the anionic surfactant is a fatty amidesulfonate having a structure selected from the group consisting of:


7. The blend of claim 1 comprising from 0.2 to 5 moles of the anionicsurfactant per mole of the cationic surfactant.
 8. A surfactant blendcomprising: (a) a cationic surfactant; and (b) an anionic surfactantmade by sulfonating an imidazoline quat, wherein the imidazoline quat isselected from the group consisting of:


9. The blend of claim 8 wherein the anionic surfactant is an imidazolinequat sulfonate having a structure selected from the group consisting of:


10. The blend of claim 8 wherein the cationic surfactant is aquaternized fatty amine or a quaternized fatty amidoamine.
 11. The blendof claim 8 wherein the cationic surfactant is cetrimonium chloride or amixture of an alkyl dimethyl benzyl ammonium chloride and an alkyldimethyl ethylbenzyl ammonium chloride.
 12. The blend of claim 8comprising from 0.2 to 5 moles of the anionic surfactant per mole of thecationic surfactant.
 13. A surfactant blend comprising: (a) a cationicsurfactant; and (b) an anionic surfactant selected from the groupconsisting of: (i) sulfonated fatty ester alkoxylates made bysulfonating an alkoxylated fatty ester having the formula:R²—CO—O-(AO)_(n)—R¹ wherein R¹ is C₁-C₄ alkyl; AO is C₂-C₄ oxyalkylene;R² is R³—C₉H₁₆— or R¹(AO)_(n)O—CO—C₁₆H₃₀—; R³ is hydrogen or C₁-C₇alkyl; and n, which is the average number of oxyalkylene units, has avalue within the range of 1 to 100; (ii) sulfonated amidoamine oxidesmade by sulfonating an amidoamine oxide of the formula:

(iii) sulfonated amidoamine oxides having the structure:

(iv) sulfonated amidoamine betaines made by sulfonating an amidoaminebetaine having the formula:R⁴(R³)(R²)N⁺(CH₂)_(n)NH(CO)R¹ wherein: R¹ is —C₉H₁₆—R⁵ or—C₁₆H₃₀—(CO)NH(CH₂)_(n)N⁺(R²)(R³)R⁴; each of R² and R³ is independentlysubstituted or unsubstituted alkyl, aryl, alkenyl, oxyalkylene, orpolyoxyalkylene; R⁴ is C₂-C₄ alkylene carboxylate; R⁵ is hydrogen orC₁-C₇ alkyl; and n=2 to 8; and (v) a sulfonated fatty amidoamine quathaving the formula:


14. The surfactant blend of claim 13 wherein the alkoxylated fatty esterused to make the sulfonated fatty ester alkoxylate has a formulaselected from the group consisting of:

where n has a value from 1 to
 100. 15. The surfactant blend of claim 13wherein the sulfonated fatty ester alkoxylate has a formula selectedfrom the group consisting of:

where n has a value from 1 to
 100. 16. The surfactant blend of claim 13wherein the amidoamine betaine used to make the sulfonated amidoaminebetaine has a formula selected from the group consisting of:


17. The surfactant blend of claim 13 wherein the sulfonated amidoaminebetaine has a formula selected from the group consisting of:


18. The blend of claim 13 wherein the cationic surfactant is aquaternized fatty amine or a quaternized fatty amidoamine.
 19. The blendof claim 13 wherein the cationic surfactant is cetrimonium chloride or amixture of an alkyl dimethyl benzyl ammonium chloride and an alkyldimethyl ethylbenzyl ammonium chloride.
 20. The blend of claim 13comprising from 0.2 to 5 moles of the anionic surfactant per mole of thecationic surfactant.